Fluorocarbon polymers and processes for their preparation

ABSTRACT

A fluorocarbon polymer comprising a perfluorocarbon main chain and a pendant chain attached to the main chain, characterized in that the pendant chain has a quaternary ammonium type terminal group.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel quaternary ammonium type polymersuseful as highly durable anion exchangers and to novelnitrogen-containing fluorocarbon polymers useful as intermediates forthe preparation of the quaternary ammonium type polymers. The presentinvention also relates to processes for preparing such novel polymers.

2. Description of the Prior Art

Anion exchangers, particularly membrane-type anion exchangers, arepractically used in the fields of e.g. electrodialysis, diffusionanalysis and various electric cells.

For such membrane-type ion exchangers, it has been common to employ acopolymer or a polymer mixture obtainable by a various combination ofhydrocarbon monomers, to which anion exchange groups have beenintroduced by a polymer reaction.

However, such conventional anion exchangers are likely to be materiallydeteriorated when subjected to severe conditions, for instance, whenused in the presence of e.g. chlorine or a strong base, or whensubjected to the repetition of swelling and contruction. Therefore, itis desired to develop an anion exchanger which is durable even undersuch severe conditions.

As a membrane-type anion exchanger developed to improve the durability,there has been known an exchanger prepared by mixing a fluorinatedpolymer such as poly(tetrafluoroethylene) and an inorganic anionexchanger such as a hydrate of zirconium oxide, and press-molding themixture (Japanese Unexamined Patent Publication No. 35079/1975).However, the ion exchange capacity of an inorganic anion exchangercomposed of such an amphoteric metal oxide is usually largely dependenton the hydrogen ion concentration in the environment in which it isused. In some cases, an inversion of the ion exchange ability will takeplace. For instance, the hydrate of zirconium oxide acts as an anionexchanger at a pH of 6 or less, but it acts as a cation exchanger at apH greater than 6 and, it exhibits no substantial ion exchange abilityunder a neutral condition. Thus, the condition under which themembrane-type anion exchanger comprising such an ion exchanger may beused, is substantially restricted.

It is also known to obtain a durable membrane by fluorinating thesurface of a hydrocarbon anion exchange membrane (Japanese UnexaminedPatent Publication No. 4489/1977). However, according to this method, itis usually difficult to accomplish adequate fluorination, and it isthereby hardly possible to obtain an anion exchange membrane havingadequate properties required for practical industrial purposes.

In view of the superior durability of the fluorinated polymer, thepresent inventors have conducted extensive researches to develop ananion exchanger using the fluorinated polymer as the base material, andhave invented a quaternary ammonium type polymer which is useful as ananion exchanger having superior durability and a process for itspreparation. The present inventors have also found novelnitrogen-containing fluorocarbon polymers which are useful asintermediates for the preparation of the quaternary ammonium typepolymer, and processes for their preparation.

SUMMARY OF THE INVENTION

The present invention provides a quaternary ammonium type polymercomprising a perfluorocarbon main chain and a pendant chain attached tothe main chain, characterized in that the pendant chain has a quaternaryammonium type terminal group represented by the formula: ##STR1## (whereeach of R¹ and R² is a lower alkyl group, an aromatic group or ahydroxy-lower alkyl group, or R¹ and R² together form a tetramethyleneor pentamethylene group, R³ is a lower alkyl group, and Z is a counterion for the quaternary ammonium ion), ##STR2## (where R⁴ is a loweralkyl group, and R³ and Z are as defined above), ##STR3## (where R⁵ is ahydrogen atom or a lower alkyl group, each of R⁶ and R⁷ is a lower alkylgroup, or R⁶ and R⁷ together form a tetramethylene or pentamethylenegroup, and R³ and Z are as defined above), or ##STR4## (where R⁸ is alower alkyl group, a is an integer of 3 to 5, and R³, R⁶, R⁷ and Z areas defined above).

DESCRIPTION OF THE PRIOR ART

The quaternary ammonium type polymer can be prepared by a process whichcomprises reacting a nitrogen-containing fluorocarbon polymer comprisinga perfluorocarbon main chain and a pendant chain attached to the mainchain and having a terminal group represented by the formula:

    --CH.sub.2 --Y                                             (II)

where Y is ##STR5## (where each of R^(1') and R^(2') is a hydrogen atom,a lower alkyl group, an aromatic group or a hydroxy-lower alkyl group,or R^(1') and R^(2') together form a tetramethylene or pentamethylenegroup), ##STR6## (where R⁴ is a lower alkyl group), or ##STR7## (whereR⁵ is a hydrogen atom or a lower alkyl group, each of R⁶ and R⁷ is alower alkyl group, or R⁶ and R⁷ together form a tetramethylene orpentamethylene group, and b is an integer of 2 to 5), with an alkylatingagent to convert the terminal group of the formula II to the terminalgroup of the formula I.

The nitrogen-containing fluorocarbon polymer having terminal groups ofthe formula II, is a novel intermediate. It can be prepared by a processwhich comprises reacting a fluorocarbon polymer comprising aperfluorocarbon main chain and a pendant chain attached to the mainchain and having a carboxylic acid amide terminal group represented bythe formula: ##STR8## where Y is as defined above, with a reducing agentto convert the terminal group of the formula III to the terminal groupof the formula II.

The nitrogen-containing fluorocarbon polymer having terminal groups ofthe formula III, is also a novel polymer. It can be prepared by aprocess which comprises reacting a fluorocarbon polymer comprising aperfluorocarbon main chain and a pendant chain attached to the mainchain and having a substituted carbonyl terminal group represented bythe formula: ##STR9## where W is a halogen atom, a hydroxyl groupunsubstituted or substituted by a tri(lower alkyl)silyl group or anammonium group, or a lower alkoxy group, with ammonia or an aminerepresented by the formula:

    H--Y                                                       (V)

where Y is as defined above, to convert the terminal group of theformula IV to the terminal group of the formula III.

In this specification, the pendant chain is meant for a substituted orunsubstituted alkyl group, a perfluoro alkyl group or an aromatic group,which is attached to a main chain of a perfluorocarbon polymer. A heteroatom or an organic ring may be present between the carbon-carbon bond ofthe pendant chain.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now, the present invention will be described in detail with reference tothe preferred embodiments.

In a typical quaternary ammonium type polymer of the present invention,the pendant chains have a structure represented by the formula:##STR10## where X is a fluorine atom, a chlorine atom or a --CF₃ group,l is an integer of 0 to 5, m is 0 or 1, n is an integer of 1 to 5, and,Q is as defined above. The integers l, m and n may be the same ordifferent among the pendant groups. Namely, the respective pendantgroups have the same integers, l, m and n when they are derived from thesame fluoroolefin monomer, whereas they have different integers l, m andn when they are derived from different fluoroolefin monomers, as in thecase of a copolymer prepared by copolymerizing at least two fluoroolefinmonomers having different l, m and n with a principal chain-formingperfluorocarbon monomer.

In the quaternary ammonium type polymer of the present invention, themain chain is preferably a linear perfluorocarbon random polymer chainwhich comprises repeating units represented by the formula: ##STR11##where p is an integer of 3 to 16, q is an integer of 1 to 10, and theratio of p'/q' is within a range of from 2 to 16 where p' is an averagevalue of all p in the repeating units and q' is an average value of allq in the repeating units.

Accordingly, a preferred quaternary ammonium type polymer of the presentinvention comprises repeating units represented by the formula:##STR12## where p, q, X, l, m, n and Q are as defined above. In theabove formula.

The quaternary ammonium type terminal group of the pendant chain isrepresented by the formula --CH₂ --Q.

Q is selected from the group consisting of: ##STR13## where each of R¹and R² is a lower alkyl group such as methyl, ethyl, n- or i-propyl, orn-, i-, s- or t-butyl; an aromatic group such as phenyl, tolyl,p-chlorophenyl, p-methoxyphenyl, furyl or thienyl; or a hydroxy-loweralkyl group such as 2-hydroxyethyl, 2-hydroxy-n-propyl or3-hydroxy-n-propyl; or R¹ and R² together form a tetramethylene orpentamethylene group; R³ is a lower alkyl group such as methyl, ethyl,n- or i-propyl, or n-, i-, s- or t-butyl, which is derived from analkylating agent mentioned hereinafter; and Z is a counter ion for thequaternary ammonium ion, e.g. an anion of a halogen atom such as bromineor iodine; a super strong acid ion such as tetrafluoroborate ion,hexachloroantimonic acid ion or a trifluoromethanesulfonic acid; asulfonic acid ion such as a benzenesulfonic acid ion or atoluenesulfonic acid ion; a carboxylic acid ion such as an acetic acidion; or a monoalkylsulfuric acid ion; ##STR14## where R⁴ is a loweralkyl group such as methyl, ethyl, n- or i-propyl, or n-, i-, s- ort-butyl; and R³ and Z are as defined above; ##STR15## where R⁵ is ahydrogen atom; or a lower alkyl group such as methyl, ethyl, n- ori-propyl, or n-, i-, s- or t-butyl; each of R⁶ and R⁷ is a lower alkylgroup such as methyl, ethyl, n- or i-propyl, or n-, i-, s- or t-butyl;or R⁶ and R⁷ together form a tetramethylene or pentamethylene group; andR³ and Z are as defined above; and ##STR16## where R⁸ is a lower alkylgroup such as methyl, ethyl, n- or i-propyl, or n-, i-, s- or t-butyl; ais an integer of 3 to 5; and R³, R⁶, R⁷ and Z are as defined above.

From the viewpoint of usefulness as the ion-exchanger, it is mostpreferred that the pendant chain has terminal groups of the formulae:##STR17## in terms of much higher resistance of the resulting ionexchanger to chlorine, ##STR18## in terms of much higher resistance tobases and ##STR19## in terms of much lower electric resistance. In theformulae R¹, R², R³, R⁶, R⁷, R⁸, a and Z are as defined above.

Particularly preferred specific terminal groups are ##STR20##

The quaternary ammonium type fluorocarbon polymer of the presentinvention may have, for example, the following repeating units:##STR21##

The quaternary ammonium type fluorocarbon polymer of the presentinvention has a excellent physical strength, dimension stability andtoughness, and further a favorable flexibility especially in the form ofmembrane.

The quaternary ammonium type fluorocarbon polymer of the presentinvention contains a hydrocarbon group as a part thereof. Nevertheless,it is extremely resistant to oxidation, particularly oxidation bychlorine and shows superior resistance to solvents and bases. Further,even when subjected to the repetition of the contraction by drying andthe swelling in a solvent (inclusive of water), it undergoes nosubstantial property change, and its handling is very easy as comparedwith conventional anion exchangers. For instance, in the form of amembrane, the quaternary ammonium type polymer of the present inventionis useful for applications for which conventional anion exchangemembranes are hardly useful, e.g. as a diaphragm for an organicelectrolytic reaction, or as a membrane for various dialyses conductedunder severe conditions. It is useful in various forms as a resin whichis capable of performing anion exchange with the quaternary ammoniumions in the presence of various solvents. Furthermore, it is useful as acatalyst for various reactions, for instance, as a catalyst for thesynthesis of cyanohydrin, as a phase transfer catalyst, or as ahalogenation reaction catalyst.

Further, in a tubular form, the quaternary ammonium polymer may beemployed as a multi-tube module in a space-saving dialysis apparatus. Itis useful also for an undesirable anion removal system in an ionchromatography. As opposed to conventional cross-linked type anionexchangers, the anion exchanger of the quaternary ammonium type polymerof the present invention is a non-cross-liked type, and accordingly, itcan readily be adapted to a change of the environment in which it isused.

The anion exchange membrane of the present invention may have a greaternumber of ion exchange groups per a pendant group, which results in alower membrane resistance, than the membrane from which it is prepared,and thus providing an advantage that it gives a low cell voltage, whenused for electrolysis.

Thus, the quaternary ammonium type polymer of the present invention hasa significant industrial value by virtue of the superior durability,etc.

It is known that a fluorinated polymer, particularly a perfluorocarbonpolymer, is far superior in the heat resistance and the chemicalresistance to common hydrocarbon polymers. Whereas, the quaternaryammonium type polymer of the present invention has an unexpectedly highdurability in spite of the fact that its pendant chains containhydrocarbon groups. Namely, while the main chain may be stabilized byits nature as a perfluorocarbon polymer chain, it has been expectedimpossible to avoid a degradation or decomposition of the hydrocarbongroups in the pendant groups and the consequential elimination of thefunctional groups if the polymer is subjected to severe conditions.Therefore, it has been totally unexpected that the quaternary ammoniumtype polymer containing hydrocarbon groups is substantially free fromsuch degradation.

The quaternary ammonium type fluorocarbon polymer having terminal groupsof the formula I is prepared by a process which comprises reacting anovel nitrogen-containing fluorocarbon polymer comprising aperfluorocarbon main chain and a pendant chain attached to the mainchain and having a terminal group represented by the formula:

    --CH.sub.2 --Y                                             (II)

where Y is as defined above, with an alkylating agent to convert theterminal group of the formula II to the terminal group of the formula I.

The alkylating agent used in the above process may be represented by theformula:

    R.sup.3 A

where R³ is a lower alkyl group, as mentioned above, and A is a residualgroup of the alkylating agent other than the lower alkyl group, which isreleased at the time of the alkylation. For example, R³ may be methyl,ethyl, n- or i-propyl, or n-, i-, s- or t-butyl, and A may be an iodineatom, a bromine atom, a dimethyloxonium fluoroborate group, adiethyloxonium fluoroborate group, a dimethyloxoniumhexafluoroantimonate group, a trifluoroactic acid group, atrifluoromethanesulfonic acid group, a monomethylsulfuric acid group, ap-toluenesulfonic acid group or a p-nitrobenzenesulfonic acid group.Thus, as the alkylating agent, there may be mentioned a lower alkyliodide, bromide or ester of a strong acid, or a tri(lower alkyl)oxoniumsalt of a super acid, such as methyl iodide, ethyl bromide, n-propylbromide, n-butyl iodide, trimethyloxonium fluoroborate ((CH₃)₃ OBF₄),triethyloxonium fluoroborate ((C₂ H₅)₃ OBF₄), trimethyloxoniumhexachloroantimonate ((CH₃)₃ OSbCl₆), dimethyl sulfate, methyltrifluoroacetate, methyl trifluoromethanesulfonate, methylp-toluenesulfonate or ethyl p-nitrobenzenesulfonate.

For the alkylation, there may be employed a solvent such as methanol,ethanol, methylene chloride, chloroform, carbon tetrachloride,tetrahydrofuran, sulforane, N,N-dimethylformamide (DMF), nitromethane orN-methyl-2-pyrrolidone (NMP).

The alkylation can be conducted under conditions which are commonlyemployed in alkylation of this type. For instance, it can readily becarried out by contacting the nitrogen-containing fluorocarbon polymeras the starting material, with the alkylating agent or its solution at atemperature of from about 0° to about 100° C.

The alkylating agent is used in an amount of at least a stoichiometricamount, preferably at least twice the stoichiometric amount, relative tothe amino group to be converted to the quaternary ammonium group. Inorder to let the reaction proceed quickly and completely, it is commonto employ the alkylating agent in a large excess amount.

When a solvent is employed, it is advisable to use it in a sufficientamount so that the fluorocarbon polymer is adequately immersed therein.

The alkylation reaction rate may vary depending upon the species of thealkylating agent used, reaction conditions such as the temperature, thesolvent, etc., but it may usually be conducted under the above-mentionedconditions for about 10 hours to about 5 days.

In the case where the terminal group of the formula ##STR22## isconverted to ##STR23## by the alkylation, if R^(1') and R^(2') are loweralkyl groups, R¹ and R² will be the same as R^(1') and R^(2'),respectively, whereas if R^(1') and R^(2') are hydrogen atoms, they willbe substituted by R³ of the alkylating agent, i.e. R¹ and R² will be thesame as R³ derived from the alkylating agent.

Likewise, in the case where the pendant group of the formula: ##STR24##is converted to ##STR25## by the alkylation, if R⁵ is a lower alkylgroup, R⁸ will be the same as R⁵, whereas if R⁵ is a hydrogen atom, itwill be substituted by R³ of the alkylating agent, i.e. R⁸ will be thesame as R³ derived from the alkylating agent.

R³ is a lower alkyl group derived from the alkylating agent. Z is acounter ion for the quaternary ammonium ion, which is usually derivedalso from the alkylating agent. As such a counter ion, there may bementioned an anion of a halogen atom, such as bromine or iodine, a superstrong acid ion such as a tetrafluoroborate ion, a hexachloroantimonicacid ion or a trifluoromethanesulfonic acid ion, a sulfonic acid ionsuch as a benzenesulfonic acid ion or a toluenesulfonic acid ion, acarboxylic acid ion such as an acetic acid ion, or a monoalkylsulfuricacid ion. These counter ions may be substituted by other ions, as thecase requires. The substitution of ions can readily be made by aconventional method, for example, by treating the quaternary ammoniumtype fluorocarbon polymer obtained by the process of the presentinvention, with an alkali metal salt such as NaCl, LiCl, LiBr, LiI,NaOH, KOH, NaNO₃ or K₂ SO₄.

The starting material fluorocarbon polymer having terminal groups of theformula II may be used in any desired form such as in a flat membraneform, a tubular form, a fiber form or a powder form, whereby the finalquaternary ammonium type polymer is obtainable in the correspondingform. Thus, an anion exchanger of the quaternary ammonium type polymermay be obtained in any desired form by so selecting the form of thestarting material.

The nitrogen-containing fluorocarbon polymer having terminal groups ofthe formula II used as the starting material in the above process, isalso a novel polymer. It preferably has pendant groups represented bythe formula: ##STR26## where X is a fluorine atom, a chlorine atom or a--CF₃ group, l is an integer of 0 to 5, m is 0 or 1, n is an integer of1 to 5, and Y is as defined above. The integers l, m and n may be thesame or different among the pendant groups, as mentioned above withrespect to the pendant groups of the typical quaternary ammonium typepolymer of the present invention.

In the nitrogen-containing fluorocarbon polymer, the main chain ispreferably a linear perfluorocarbon random polymer chain which comprisesrepeating units represented by the formula: ##STR27## where p is aninteger of 3 to 16, q is an integer of 1 to 10, and the ratio of p'/q'is within a range of from 2 to 16 where p' is an average value of all pin the repeating units and q' is an average value of all q in therepeating units.

Accordingly, a preferred nitrogen-containing fluorocarbon polymer havingterminal groups of the formula II comprises repeating units representedby the formula: ##STR28## where p, q, l, m, n, X and Y are as definedabove.

The terminal group of the nitrogen-containing fluorocarbon polymer isrepresented by the formula --CH₂ --Y where Y is selected from the groupconsisting of ##STR29## where each of R^(1') and R^(2') is hydrogenatom; a lower alkyl group such as methyl, ethyl, n- or i-propyl, or n-,i-, s- or t-butyl; an aromatic group such as phenyl, tolyl,p-chlorophenyl, p-methoxyphenyl, furyl or thienyl; or a hydroxy-loweralkyl group such as 2-hydroxyethyl, 2-hydroxy-n-propyl or3-hydroxy-n-propyl; or R^(1') and R^(1') together form a tetramethyleneor pentamethylene group; ##STR30## where R⁴ is a lower alkyl group suchas methyl, ethyl, n- or i-propyl, or n-, i-, s- or t-butyl; ##STR31##where R⁵ is a hydrogen atom, a lower alkyl group such as methyl, ethyl,n- or i-propyl, or n-, i-, s- or t-butyl; each of R⁶ and R⁷ is a loweralkyl group such as methyl, ethyl, n- or i-propyl, or n-, i-, s- ort-butyl; or R⁶ and R⁷ together form a tetramethylene or pentamethylenegroup; and b is an integer of 2 to 5.

The nitrogen-containing fluorocarbon polymer having terminal groupsrepresented by the formulae: ##STR32## where R^(1'), R^(2'), R⁵, R⁶, R⁷and b are as defined above, is especially preferred, since it provides asuperior quaternary ammonium type polymer of the present invention.

Particularly preferred specific terminal groups are ##STR33##

The fluorocarbon polymer having terminal groups of the formula II mayhave, for example, the following repeating units: ##STR34##

The nitrogen-containing fluorocarbon polymer having terminal groups ofthe formula II is a solid substance having excellent heat resistance,acid resistance and alkali resistance, and can be formed into variousforms such as a flat membrane form, a fiber form, a tubular form or apowder form. It is useful not only as the starting material for thequaternary ammonium type polymer, but also as a weakly basic anionexchange membrane having superior durability by itself.

The nitrogen-containing fluorocarbon polymer having terminal groupsrepresented by the formula --CH₂ Y (II) can be prepared by a processwhich comprises reacting a fluorocarbon polymer comprising aperfluorocarbon main chain and a pendant chain attached to the mainchain and having a carboxylic acid amide terminal group represented bythe formula: ##STR35## where Y is as defined above, with a reducingagent to convert the terminal group of the formula III to the terminalgroup of the formula II.

As the reducing agent, there may be used aluminum hydride, an alkylaluminum hydride such as diisobutyl aluminum hydride, a halogenoaluminum hydride such as monochloro aluminum hydride, lithium aluminumhydride or diborane. However, it is preferred to use diborane in view ofthe efficiency of the reaction and the convenience of thepost-treatment. Borane may be generated in the reaction system byreacting e.g. sodium borohydride with a boron trifluoride ether complex,or it may be added to the reaction system in the form of variouscomplexes of borane (e.g. in the form of a dimethyl sulfide complex).

The reducing agent is used in an amount of at least a stoichiometricamount relative to the functional groups, i.e. the carboxylic acid amidegroups, in the fluorocarbon polymer. Usually it is used in asubstantially excess amount. Its concentration in a solvent is usuallyfrom 0.01 to 5M, preferably from 0.1 to 2M.

The reaction proceeds smoothly when conducted in a solvent such astetrahydrofuran, dioxane or an ether such as diethylene glycol dimethylether. The solvent is used in a sufficient amount so that thefluorocarbon polymer having the carboxylic acid amide terminal groups isadequately immersed therein. It may be used in a substantially excessamount.

The reaction temperature is not critical. However, it is preferred thatat the initial stage, the reaction is conducted at a temperature of from0° C. (i.e. ice cooling temperature) to room temperature, and then thereaction system is heated to a temperature of from the refluxingtemperature to 100° C. to complete the reaction.

The starting material fluorocarbon polymer having the substitutedcarbonyl groups of the formula III may be used in any desired form suchas in a flat membrane form, a tubular form, a fiber form or a powderform, whereby the resulting polymer having the terminal amino groups ofthe formula II is obtainable in the corresponding form, which may thenbe converted, in that form, to the final quaternary ammonium typepolymer by the above-mentioned alkylation. Thus, the anion exchanger ofthe quaternary ammonium type polymer may be obtained in any desired formby so selecting the form of the starting material.

The fluorocarbon polymer having the terminal groups of the formula IIIused as the starting material, is also a novel polymer. A typicalpendant chain of the fluorocarbon polymer has a structure represented bythe formula: ##STR36## where X is a fluorine atom, a chlorine atom or a--CF₃ group, l is an integer of 0 to 5, m is 0 or 1, n is an integer of1 to 5, and Y is as defined above.

The main chain is preferably a linear perfluorocarbon random polymerchain comprising repeating units represented by the formula: ##STR37##where p is an integer of 3 to 16, q is an integer of 1 to 10, and theratio of p'/q' is within a range of from 2 to 16 where p' is an averagevalue of all p in the repeating units and q' is an average value of allq in the repeating units.

Accordingly, a preferred fluorocarbon polymer having terminal groups ofthe formula III has repeating units represented by the formula:##STR38## where p, q, l, m, n, X and Y are as defined above.

Among the various terminal groups represented by the formula ##STR39##particularly preferred is a terminal group represented by the formula:##STR40## where R⁵, R⁶, R⁷ and b are as defined above.

Particularly preferred specific terminal groups are ##STR41##

The fluorocarbon polymer having terminal groups of the formula III mayhave, for instance, the following repeating units: ##STR42##

The novel fluorocarbon polymer having terminal groups of the formula##STR43## (III) may be prepared by a process which comprises reacting afluorocarbon polymer comprising a perfluorocarbon main chain and apendant chain attached to the main chain and having a substitutedcarbonyl terminal group represented by the formula: ##STR44## where W isa halogen atom such as fluorine, chlorine or bromine; an unsubstitutedhydroxy group; a hydroxy group substituted by a tri(lower alkyl)silylgroup such as trimethylsilyloxy, triethylsilyloxy group; a hydroxy groupsubstituted by an ammonium group such as ##STR45## which constitutes apart of a carboxylic acid ammonium salt together with a carbonyl group##STR46## or a lower alkoxy group such as methoxy, ethoxy, n-propoxy,n-butoxy, s-butoxy or n-pentoxy; with ammonia or an amine represented bythe formula:

    H--Y                                                       (V)

where Y is as defined above, to convert the terminal group of theformula IV to the terminal group of the formula III.

The fluorocarbon polymer having terminal groups of the formula IV usedas the starting material preferably has pendant chains represented bythe formula: ##STR47## where X, W, l, m and n are as defined above.

A typical main chain of the polymer is a linear perfluorocarbon randompolymer chain which comprises repeating units represented by theformula: ##STR48## where p is an integer of 3 to 15, and q is an integerof 1 to 10.

Accordingly, a preferred polymer has repeating units represented by theformula: ##STR49## where X, W, l, m, n, p and q are as defined above.

As specific examples of the fluorocarbon polymer having substitutedcarbonyl terminal groups of the formula IV, there may be mentioned thosehaving the following repeating units: ##STR50##

These fluorocarbon polymers are well known as carboxylic acid typecation exchange perfluorocarbon polymers (particularly as cationexchange membranes for the electrolysis of sodium chloride) or as theirprecursors.

Among the fluorocarbon polymers, those having pendant chains with acidhalide type terminal groups may readily be prepared by treatingperfluorocarbon polymers having pendant chains with terminal carboxylgroups (i.e. those having the above formula wherein W is a hydroxylgroup), with a halogenating agent such as a chlorinating agent. As thechlorinating agent, there may be employed thionyl chloride, phosphorustrichloride, phosphorus pentachloride or phosphorus oxychloride.However, from the viewpoint of the reaction efficiency, it is preferredto use thionyl chloride or phosphorus chloride in phosphorusoxychloride. The reaction temperature is usually within a range of from50° to 150° C. although it depends on the nature of the startingmaterial and the chlorinating agent.

Whereas, silyl ester type fluorocarbon polymers may be prepared bytreating the above-mentioned carboxylic type polymer with a silylatingagent such as a tri(lower alkyl)silyl chloride or an N,O-bis[tri(loweralkyl)silyl]acetamide.

As the amine of the formula V to be used for the above reaction, theremay be mentioned methylamine, ethylamine, n-propylamine, i-propylamine,n-butylamine, i-butylamine, dimethylamine, diethylamine, dipropylamine,methylethylamine, pyrrolidine, piperidine, pipecoline,3-ethylpiperidine, aniline, N-methylaniline, p-toluidine, m-toluidine,p-chloroaniline, m-chloroaniline, p-fluoroaniline, o-fluoroaniline,p-bromoaniline, p-anisidine, m-anisidine, p-dimethylaminoaniline,m-nitroaniline, 2-aminofuran, 3-aminofuran, ethanolamine,diethanolamine, 3-hydroxypropylamine, 3-hydroxybutylamine,N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine,N-ethyl-N-methyl-1,3-propanediamine,N-isobutyl-N-methyl-1,3-propanediamine,N,N,N-trimethyl-1,3-propanediamine,N,N-dimethyl-N'-propyl-1,3-propanediamine,N-(3-aminopropyl)-2-pipecoline, 3-pyrrolidinopropylamine,3-piperidinopropylamine, N,N-dimethyl-1,4-butanediamine orN,N-dimethyl-1,5-pentanediamine. Instead of these amines, thecorresponding silyl amines obtained by substituting the hydrogen atomson the nitrogen atoms of the amine of the formula V by a trimethylsilylgroup, may also be used.

The reaction with the amine may be conducted by contacting the polymerwith a gaseous amine, or in a liquid amine or by means of a solvent.

When a polymer other than an acid halide type polymer or an ester typepolymer is used as the starting material for the reaction, it ispreferred to employ a silylating agent such as trimethylchlorosilane,bis(trimethylsilyl)acetamide or 1,1,1,3,3,3-hexamethyldisilazane,together with the amine of the formula V. Particularly when the firstsilylating agent is used, it is preferred to conduct the reaction in thepresence of a tertiary amine such as triethyl amine orN-methylpyrrolidine.

The ammonia or the amine is used in an amount of at least astoichimetric amount, preferably at least three times the stoichiometricamount, more preferably in a great excess, relative to the startingmaterial. The reaction may be conducted in the presence of a tertiaryamine.

As the solvent, there may be employed an ether such as diethyl ether,tetrahydrofuran, dimethoxyethane or dioxane; a hydrocarbon such asbenzene, toluene or hexane; acetonitrile; or dimethylsulfoxide. When afluorocarbon polymer having terminal groups of the formula IV where W isa lower alkoxy group, is used, i.e. when the terminal group of thependant chain is a carboxylic acid ester type, it is possible to employnot only the above-mentioned solvents but also alcohols such as methanolor ethanol.

The solvent is used in a sufficient amount so that the fluorocarbonpolymer having the substituted carbonyl groups is adequately immersedtherein. It may be used in an excess amount.

The reaction temperature is not critical. However, it is common toconduct the reaction at a temperature of from about -30° C. to about150° C., preferably from about 0° C. to 80° C.

DESCRIPTION OF THE DRAWINGS

In the accompanying drawing, FIG. 1 shows current-voltage curves in theelectrolysis of hydrochloric acid by means of the membrane obtained inExample 3 and a commercially available hydrocarbon type anion exchangemembrane.

Now, the present invention will be described in further detail withreference to Examples and Reference Examples. The term "an amine typepolymer" used here is meant for a nitrogen-containing fluorocarbonpolymer containing amino groups, and the term "an amide type polymer" ismeant for a fluorocarbon polymer having carboxylic acid amide groups.Furmat, the term "a terminal group" used here is meant for a terminalgroup of the pendant chain. The infrared absorption spectrum means atransmission spectrum unless otherwise specified. The dyeing test wasconducted by using the following dye baths.

Crystal Violet: a 0.05% methanol solution of Crystal Violet

Cresol Red: a 0.05% methanol solution of Cresol Red

Thymol Blue: a 0.05% methanol solution of Thymol Blue

Bromothymol Blue: a 0.05% methanol solution of Bromothymol Blue

Basic Cresol Red: a solution obtained by adding about 1% of a 10% NaOHaqueous solution to a 0.05% water-methanol solution of Cresol Red

Basic Thymol Blue: a solution obtained by adding about 1% of a 10% NaOHaqueous solution to a 0.05% methanol solution of Thymol Blue

The electric resistance of a membrane was measured in a 0.5N NaClaqueous solution at alternating current of 1000 cycles at a temperatureof 25° C. after bringing the membrane to equilibrium in the 0.5N NaClaqueous solution. The transport number of a membrane was calculated fromthe membrane potential generated between a 0.5N NaCl aqueous solutionand a 2.0N aqueous solution, by means of a Nernst's equation.

The ion exchange capacity of an ammonium-type polymer was obtained bysubjecting an ammonium chloride type polymer to complete salt exchangeand then quantitatively analyzing chlorine ions which were present inthe polymer as counter ions, according to Vorhard method.

The conversion was calculated from the nitrogen value obtained from theelemental analysis, taking into accounts of the change of the equivalentof weight due to the conversion of the terminal groups and taking theion exchange capacity of the starting material copolymer as being 100%.

EXAMPLES EXAMPLE 1

A copolymer film [Nafion 114 (tradename) manufactured by Dupont Co.;film thickness: 100 μm; sulfonic acid-based ion-exchange capacity: 0.91meq/g.dry film] obtained by the copolymerization of CF₂ ═CF₂ with##STR51## was treated with 2N hydrochloric acid and then converted to asulfonylchloride form, which was further subjected to hydrogen-iodidetreatment and then to washing with alkali, whereby a membrane of asodium carboxylate type copolymer. The pendant chains of thismembrane-form copolymer had a structure of ##STR52##

This membrane was treated withh a mixture of 8N hydrochloricacid/methanol (volume ratio of 1/1) for hydrolysis and esterificationand then heated in a mixture of phosphorus pentachloride/phosphorusoxychloride (weight ratio of 1/1.6) at 120° C. for 24 hours. Then, themembrane was washed in carbon tetrachloride and dried. In its infraredabsorption spectrum, the membrane thus obtained showed a strongabsorption by carbonyl at 1800 cm⁻¹ and absorption peaks in the vicinityof 2980, 2880 and 1440 cm⁻¹ attributable to the absorption by C--H.Thus, the membrane was found to be a mixture-type polymer membranewherein the majority of terminal groups of the pendant chains were --CO₂Me groups and some --COCl groups were mixed therein.

This mixture-type polymer membrane was composed mainly of repeatingunits having a structure of the formula (1) identified hereinafter,wherein W is a methoxy group. The ratio of p'/q' was about 6.5.

The mixture-type polymer membrane thus obtained was immersed in driedether, and dimethylamine gas was introduced (concentration of 1.3M)under cooling with ice, whereupon the membrane was reacted therewith for6 hours under cooling and 18 hours at room temperature. The membrane waswashed with a mixture of a 3% sodium bicarbonate aqueoussolution/methanol (volume ratio of 1/1) at 80° C. for 5 hours, and thendried under reduced pressure over night, whereby a colorless transparentamide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3300, 2950, 2825, 2360, 1705, 1500,1470, 1410, 1300-1100, 980, 920, 730, 650-610, 560-600.

The absorption by C--H was observed at 2950 and 1500-1410 cm⁻¹, and theabsorption by amide carbonyl was observed at 1705 cm⁻¹. The conversioncalculated from the nitrogen value obtained by the elemental analysiswas 92% relative to the SO₃ H-based exchange capacity. The amide-typepolymer membrane thus obtained was not dyed by Crystal Violet or CresolRed, thus indicating that no ionic groups were present in the membrane.

This membrane was composed mainly of repeating units represented by theformula (101) identified hereinafter. The ratio of p'/q' was about 6.5.

This membrane was immersed in a solution obtained by dissolving sodiumborohydride (concentration of 0.53M) in dried diethylene glycol dimethylether under an argon atmosphere. A dried diethylene glycol dimethylether solution of boron trifluoride ether complex (0.62 molar equivalentto the sodium borohydride) was dropwise added under cooling with ice.The reaction was conducted for 5 hours under cooling and 18 hours at100° C., whereby the absorption at 1700 cm⁻¹ in the infrared absorptionspectrum disappeared, thus indicating that the reduction to anamine-type polymer proceeded completely. The membrane thus obtained waswashed with methanol and dried, whereupon the infrared absorptionspectrum was measured. The conversion was 88%.

Infrared absorption spectrum (cm⁻¹) 2970, 2850, 2800, 2360, 1475-1455,1395, 1350-1040, 980, 930, 860, 835, 730, 640-610, 560-490.

The amine-type polymer membrane thus obtained was not dyed by CrystalViolet or Cresol Red. Thus it was found that no ionic groups werepresent in the membrane.

This membrane was an amine-type polymer composed substantially ofrepeating units represented by the formula (201) identified hereinafter.The ratio of p'/q' was about 6.5.

The amine-type polymer membrane thus obtained was immersed in a solutionof methyl iodide/methanol (volume ratio of 1/4) and reacted at 60° C.for 48 hours. The membrane obtained was washed with methanol and thenreacted in a methanol solution of lithium chloride (concentration of1.28M) at 60° C. for 24 hours. This membrane was heated to 60° C. inmethanol, whereby a quaternary ammonium chloride-type copolymer membranewas obtained. In the dyeing test, the membrane thus obtained was notdyed by Crystal Violet, but it was dyed red (bluish purple in basicwater) with Bromocresol Purple and yellowish orange (reddish purple inbasic water) with Cresol Red. Thus, the presence of anion exchangegroups was confirmed.

Infrared absorption spectrum (cm⁻¹) 3300, 3030, 2950, 2810, 2350, 1640,1485, 1415, 1300-1060, 980, 925, 840, 740, 650-600, 540-500.

The absorption at 3300 and 1640 cm⁻¹ is considered attributable to watercontained in the membrane. This cation exchange membrane had an ionexchange capacity of 0.82 meq/g.dry membrane, an electric resistance of3.3 Ωcm² and a transport number of 0.87. This membrane was composedsubstantially of repeating units having a structure of the formula (301)identified hereinafter. The ratio of p'/q' was about 6.5. No change wasobserved in these values even after immersing the membrane in an aqueoussolution saturated with chlorine at 60° C. for 1000 hours. Likewise, nochange was observed even when the membrane was treated in methanol at65° C. for 48 hours, followed by the removal of the solvent under vacuumat 40° C., and this operation was repeated 5 times.

EXAMPLE 2

A copolymer obtained by copolymerizing CF₂ ═CF₂ with ##STR53## inaccordance with a conventional method, was formed into a membrane(thickness: 110 μm; CO₂ H-based ion exchange capacity: 1.4 meq/g.drymembrane).

This polymer was composed substantially of repeating units of theformula (2) identified hereinafter, wherein W is a methoxy group. Theratio of p'/q' was about 3.1.

This methyl ester-type polymer membrane was treated with dimethyl aminein the same manner as in Example 1 to obtain a corresponding amide-typepolymer membrane (conversion: 95%). The infrared absorption spectrum ofthe membrane thus obtained, was substantially the same as the spectrumof the membrane obtained in Example 1, except for the absorption atabout 1000-800 cm⁻¹ by the skeletal portion, thus indicating that thedesired exchange of the terminal groups proceeded efficiently. Theamido-type polymer membrane thus obtained, was not dyed by CrystalViolet or Cresol Red.

This amide-type polymer was composed substantially of repeating units ofthe formula (102) identified hereinafter. The ratio of p'/q' was about3.1.

The amide-type polymer membrane was then reduced in the same manner asin Example 1, to obtain an amine-type polymer membrane. The conversionwas 95%. The infrared absorption spectrum of the membrane thus obtained,was substantially the same as that of the membrane obtained in Example1, except for the absorption by the skeletal portion, and the absorptionat about 1700 cm⁻¹ by amide carbonyl disappeared completely. Theobtained membrane was not dyed by Crystal Violet or Cresol Red.

This membrane was composed substantially of repeating units of theformula (202) identified hereinafter. The ratio of p'/q' was about 3.1.

Then, the membrane was immersed in a solution of methyl iodide/methanol(volume ratio of 1/4) and reacted at 60° C. for 48 hours. The membranethereby obtained was washed with methanol and then reacted in a methanolsolution of lithium chloride (concentrated of 1.28M) at 60° C. for 24hours. This membrane was heated to 60° C. in methanol, where the desiredammonium chloride-type membrane was obtained. In the dyeing test, themembrane thus obtained, was not dyed by Crystal Violet, and it was dyedred (bluish purple in basic water) with Bromocresol Purple and yellowishorange (reddish purple in basic water) with Cresol Red. Thus, thepresence of cation exchange groups was confirmed.

This membrane was composed substantially of repeating units of theformula (302) identified hereinafter. The ratio of p'/q' was 3.1. Themembrane had an ion exchange capacity of 1.1 meq/g.dry membrane and anelectric resistance of 1.8 Ωcm². This membrane showed superiordurability like the membrane of Example 1.

EXAMPLE 3

A film [Nafion 415 (tradename) manufactured by Dupont Co.] composed of acopolymer of CF₂ ═CF₂ with ##STR54## supported with apolytetrafluoroethylene mesh, which copolymer had a sulfonic acid-baseion exchange capacity of 0.91 meq/g.dry polymer, was treated in the samemanner as in Example 1, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3300, 2950, 2750, 2380, 1690,1500-1400, 1320-950, 760-480.

The membrane thus obtained was not dyed with Crystal Violet or CresolRed.

Except for the mesh portion, this membrane was made of a polymercomposed substantially of repeating units of the formula (101)identified hereinafter. The ratio of p'/q' was about 6.5.

The carboxylic acid amide-type polymer membrane supported with thepolytetrafluoroethylene mesh thus obtained, was subjected to the samereducing treatment as in Example 1, whereby an amine-type polymermembrane was obtained. In the infrared absorption spectrum, theabsorption at about 1700 cm⁻¹ disappeared completely.

Infrared absorption spectrum (cm⁻¹) 3200, 2950-2790, 2400-2300, 1440,1390, 1300-920, 720-480.

The obtained membrane was not dyed by Crystal Violet or Cresol Red.

Except for the mesh portion, this membrane was made of a polymercomposed substantially of repeating units of the formula (201)identified hereinafter. The ratio of p'/q' was about 6.5.

The amine-type polymer membrane thus obtained was subjected to the sametreatment as in Example 1, whereby an ammonium chloride-type polymermembrane was obtained.

Infrared spectrum absorption spectrum (cm⁻¹) 3250, 2900, 2800,2400-2300, 1620, 1470-1400, 1300-900, 750-500.

The absorption at 3250 and 1620 cm⁻¹ are considered to be attributableto water in the membrane. When subjected to dyeing treatment with CresolRed in methanol, the entire membrane except for the supporting materialwas uniformly dyed yellowish orange.

Except for the mesh portion, the obtained membrane was made of a polymercomposed substantially of repeating units of the formula (301). Theratio of p'/q' was about 6.5. This membrane had an electric resistanceof 7.2 Ωcm² and a transport number of 0.90.

This membrane was used for the electrolysis of hydrochloric acid, andthe current-voltage curve (a) thereby obtained is shown in FIG. 1. As aReference Example, the electrolysis was conducted in the same mannerexcept that instead of this membrane, a commercially availablehydrocarbon type anion exchange membrane was used, and the resultsthereby obtained are also shown in FIG. 1 (the current-voltage curve(b)). The electrolysis was conducted under the following conditions.

Membrane Surface area: 9.6 cm²

Electrodes: Platinum

Electrolytes: Anode/Cathode=6N hydrochloric acid/6N hydrochloric acid

Temperature: room temperature

It is evident from the FIGURE that the membrane obtained in this Examplehas a remarkable feature that in spite of the fact that its ion exchangecapacity is smaller than the commercially available hydrocarbon typeanion exchange membrane (ion exchange capacity: ca. 1.3 meq/g.drymembrane), its electric resistance is substantially the same as thecommercial membrane. Further, no increase of the membrane resistance orno deterioration of the membrane was observed even when the membrane wassubjected to the test for an extended period of time under suchconditions that chlorine was generated at the anode side and hydrogenwas generated at the cathode side.

EXAMPLE 4

A copolymer obtained by copolymerizing CF₂ ═CF₂ with ##STR55## wasformed into a membrane (thickness: 100 μm; SO₃ H-based ion exchangecapacity: 0.92 meq/g.dry membrane) and then hydrolyzed. Then, themembrane was treated with 2N HCl, and converted to a sulfonyl chlorideform, followed by oxidation treatment to convert the membrane to acarboxylic acid form. The carboxylic acid membrane thus obtained washeated in a mixture of phosphorus pentachloride/phosphorus oxychloride(weight ratio of 1/1.6) at 120° C. for 24 hours. The membrane wasfurther washed in carbon tetrachloride and dried. In the infraredspectrum, this membrane showed a strong absorption by carbonyl at 1800cm⁻¹.

The acid chloride membrane thus obtained was immersed in dried ether,and dimethylamine gas was introduced under cooling with ice, whereuponthe membrane was reacted therewith for 6 hours under cooling and 18hours at room temperature. The membrane was washed with a mixed solutionof a 1.5% sodium bicarbonate aqueous solution/methanol at 80° C. for 5hours and dried under reduced pressure over night. A colorlesstransparent membrane was thereby obtained. In its infrared spectrum,absorption by C--H was observed at 2930 and 1420 cm⁻¹, and absorption byamide carbonyl was observed at 1700 cm⁻¹.

Then, sodium borohydride was dissolved in dried diethylene glycoldimethyl ether under an argon atmosphere, and the membrane obtained asabove was immersed therein. A dried diethylene glycol dimethyl ethersolution of a boron trifluoride ether complex was added dropwise theretounder cooling with ice. The reaction was conducted for 5 hours undercooling and 18 hours at 100° C., whereupon the absorption at 1700 cm⁻¹in the infrared spectrum disappeared, thus indicating the reduction toan amine-type membrane proceeded completely. The membrane thus obtainedwas washed with methanol, immersed in a methanol solution of methyliodide and reacted at 60° C. for 44 hours. The membrane thereby obtainedwas washed with methanol and then reacted in a methanol solution oflithium chloride at 60° C. for 24 hours. The membrane was heated to 60°C. in methanol, whereby a membrane having the desired quaternaryammonium chloride groups was obtained. In the dyeing tests, the obtainedmembrane was dyed bluish purple with Bromocresol Purple and reddishpurple with Cresol Red. Thus, the presence of anion exchange groups wasconfirmed.

Infrared spectrum absorption (cm⁻¹) 1741, 1477, 1413, 1205, 1147, 979,933, 842, 740.

The anion exchange membrane thus obtained had an ion exchange capacityof 0.86 meq/g.dry membrane (no change of the equivalent weight was takeninto account), an electric resistance of 3.2 Ωcm² and a transport numberof 0.86. No change was observed in these values even when the membranewas immersed in an aqueous solution saturated with chlorine at 60° C.for 1000 hours.

EXAMPLE 5

The same membrane as used as the starting material in Example 2, washydrolyzed and treated with 2N HCl to convert the membrane to acarboxylic acid form (wherein W in the formula (2) was a hydroxylgroup).

By using the membrane thus obtained and dimethylamine, an anion exchangemembrane having the desired quaternary ammonium chloride groups wasobtained in the same manner as in Example 4. This membrane was made of apolymer composed substantially of repeating units of the formula (302)identified hereinafter.

The membrane had an ion exchange capacity of 1.3 meq/g.dry membrane (nochange of the equivalent weight was taken into account), an electricresistance of 3.0 Ωcm² and a transport number of 0.84. The same resultsas in Example 4 were obtained also with respect to the resistance tochlorine.

EXAMPLE 6

A copolymer obtained by copolyemrizing CF₂ ═CF₂ with ##STR56## wasformed into a tube (internal diameter: 0.625 mm; outer diameter: 0.875mm; SO₃ H-based ion exchange capacity: 0.92 meq/g.dry resin) and thenhydrolyzed. Then, the tubular polymer was treated with 2N hydrochloricacid and converted to a sulfonyl chloride form. The polymer was thentreated with hydrogen iodide and immersed in methanol to convert thetubular polymer to a carboxylic acid methyl ester form. The pendantchains of the tubular ester-type polymer obtained by the series ofoperations were converted to ##STR57##

This tubular ester-type polymer was heated in a mixture of phosphoruspentachloride/phosphorus oxychloride (weight ratio of 1/1.6) at 120° C.for 23 hours and then washed in carbon tetrachloride and dried, wherebya tubular mixture-type polymer was obtained wherein the majority of theterminal groups were ester groups and some of the terminal groups wereacid chloride groups. This polymer was composed substantially ofrepeating units of the formula (101) identified hereinafter, wherein Wwas mostly a methoxy group and partly a chlorine atom. The ratio ofp'/q' was about 6.4.

This tubular mixture-type polymer was immersed in diethyl ether, wherebythe inside of the tube was substituted by dried diethyl ether. Dimethylamine gas was introduced thereto (to the concentration of 1.3M) undercooling with ice. Then, the reaction was conducted for 6 hours undercooling and 19 hours at room temperature. Thereafter, the tubularpolymer was washed with a mixture of a 3% sodium bicarbonate aqueoussolution/methanol (volume ratio of 1/1) at 60° C. for 6 hours and driedunder reduced pressure over night. The infrared absorption spectrum ofthe tubular amide-type polymer thereby obtained was found to besubstantially the same as the spectrum of the amide-type membraneobtained in Example 1. The conversion was 90%. The tubular polymer thusobtained was cut into rings and examined for the dyeability with CrystalViolet and Cresol Red. The polymer was not dyed at all.

The amide-type polymer of this membrane was composed substantially ofrepeating units of the formula (101) identified hereinafter. The ratioof p'/q' was about 6.4.

The tubular amide-type polymer was reduced to a tubular amine-typepolymer in the same manner as in Example 26 hereinafter mentioned.

The tubular amine-type polymer thus obtained was immersed in a solutionof methyl iodide in methanol (volume ratio of 1/4) and reacted at 60° C.for 50 hours. The tubular polymer thereby obtained was washed withmethanol and reacted in a methanol solution of lithium chloride(concentration of 1.28M) at 60° C. for 24 hours. This tubular polymerwas heated to 60° C. in methanol, whereby the desired tubular ammoniumchloride-type polymer was obtained. In the dyeing test, the obtainedtubular polymer was dyed red with Bromocresol Purple and yellowishorange with Cresol Red (each in methanol). Thus, the presence of anionexchange groups was confirmed.

This membrane was made of a polymer having repeating units of theformula (301) identified hereinafter. The ratio of p'/q' was about 6.4.

The tubular anion exchanger thereby obtained had an ion exchangecapacity of 0.80 meq/g.dry resin. No change was observed in this valueeven when the anion exchanger was immersed in an aqueous solutionsaturated with chlorine at 60° C. for 100 hours. Likewise, no change wasobserved even when the exchanger was treated in methanol at 65° C. for48 hours, followed by the removal of the solvent under vacuum at 40° C.,and this operation was repeated 5 times.

EXAMPLE 7

A copolymer powder [Nafion 511 (tradename) manufactured by Dupont Co.;SO₃ H-based ion exchange capacity: 0.91 meq/g.dry resin; potassiumsulfonate-type] obtained by the copolymerization of CF₂ ═CF₂ with##STR58## followed by saponification, was hydrorized with 5Nhydrochloric acid and then treated with phosphorus pentachloride toconvert it to a sulfonyl chloride form. Then, it was subjected tohydrogen iodide treatment to convert it to a carboxylic acid form. Then,it was immersed in methanol, whereby the majority of the carboxyl groupswere converted to methoxycarbonyl groups. It was further treated withmethyl orthoformate to obtain a powder methyl ester-type polymer.

Infrared absorption spectrum (cm⁻¹) 2970-2860, 1800, 1480-1415,1280-1200, 1175-1110, 980, 840, 780, 740, 635, 555, 510.

This powder polymer was composed substantially of repeating units of theformula (1) identified hereinafter, wherein W was a methoxy group. Theratio of p'/q' was about 6.6.

This powder methyl ester-type polymer was treated in driedtetrahydrofuran in the same manner as in Example 1, whereby a powderamide-type polymer was obtained. This polymer was not dyed with CrystalViolet or Cresol Red. The conversion obtained from the elementalanalysis was 85%. The obtained powder was formed into a KBr disc andexamined for the infrared absorption spectrum, whereby an absorptionattributable to amide carbonyl was observed at about 1700 cm⁻¹.

Infrared absorption spectrum (cm⁻¹) 2960, 1710, 1410, 1280-1200,1170-1130, 1070, 980, 920, 800, 780, 740, 640, 550, 510.

This polymer was composed substantially of repeating units of theformula (101) identified hereinafter. The ratio of p'/q' was about 6.6.

The powder amide-type polymer thus obtained was reduced with diboran inthe same manner as in Example 1 and then filtered to obtain a powderamine-type polymer. This powder polymer was not dyeable with CrystalViolet and Cresol Red. The conversion was 79%. The obtained powder wasformed into a KBr disc and examined for the infrared absorptionspectrum, whereby the absorption by amido carbonyl observed at about1700 cm⁻¹ was found to have completely disappeared.

Infrared absorption spectrum (cm⁻¹) 3020-2780, 1500-1460, 1260-1200,1170-1120, 1070, 980, 930, 865, 835, 735, 635, 555, 510.

This amine-type polymer was composed substantially of repeating units ofthe formula (201) identified hereinafter. The ratio of p'/q' was about6.6.

The powder amine-type polymer thus obtained was introduced into asolution of methyl iodide in methanol (volume ratio of 1/4) and reactedat 60° C. for 50 hours. The powder polymer thus obtained was washed withmethanol and reacted in a methanol solution of lithium chloride(concentration of 1.28M) at 60° C. for 24 hours. This powder polymer washeated to 60° C. in methanol, whereby the desired powder ammoniumchloride-type polymer was obtained. In the dyeing test, the powderpolymer thus obtained was dyed reddish purple by Bromocresol Purple andyellow by Cresol Red (each in methanol). Thus, the presence of anionexchange groups was confirmed.

Infrared absorption spectrum (cm⁻¹) 3040-2820, 1530-1460, 1280-1200,1170-1100, 980, 930, 840, 740, 635, 550, 510.

This powder polymer was composed substantially of repeating units of theformula (301) identified hereinafter. The ratio of p'/q' was about 6.6.

The powder anion exchanger thereby obtained had an ion exchange capacityof 0.80 meq/g.dry resin. No change was observed in this value even whenthe anion exchanger was immersed in an aqueous solution saturated withchlorine, at 60° C. for 100 hours. Likewise, no change was observed evenwhen the anion exchanger was treated in methanol at 65° C. for 48 hours,followed by the removal of the solvent under vacuum at 40° C., and thisoperation was repeated 5 times.

EXAMPLE 8

A mixture-type polymer membrane (9 cm²) obtained in the same manner asin Examples 9 to 12, was immersed in 30 ml of dried tetrahydrofuran, andafter an addition of 4 ml of pyrrolidine, the solution was heated forrefluxing under an argon atmosphere for 44 hours. Then, the membrane wastaken out and dried under reduced pressure at 60° C. for 20 hours,whereby an amide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3400, 2970, 2890, 2780, 2600, 2360,1710-1680, 1440, 1340-1030, 980, 930, 915, 800-480.

This membrane was composed mainly of repeating units of the formula(103) identified hereinafter. The ratio of p'/q' was about 7.6.

The membrane thus obtained was then immersed in 200 ml of driedtetrahydrofuran, and 10 g of sodium borohydride was added thereto. Then,a solution of 20 ml of boron trifluoride ethyl ether complex in 5 ml oftetrahydrofuran was added dropwise in 20 minutes, and the mixture wasstirred for 1.5 hours. Thereafter, the mixture was heated for refluxingfor 65 hours, and then the membrane was taken out and washed in methanolunder heating for refluxing for 8 hours. The membrane was taken out anddried under reduced pressure at 60° C. for 20 hours, whereby anamine-type polymer membrane was obtained. From the infrared spectrum ofthis membrane, it was found that the absorption at about 1700 cm⁻¹attributable to amide carbonyl disappeared and the reduction to theamine-type membrane proceeded completely. The conversion calculated fromthe nitrogen value in its elementary analysis, was 90%. The amine-typepolymer membrane thus obtained was not dyeable with Crystal Violet,Cresol Red, Thymol Blue and Bromothymol Blue.

Infrared absorption spectrum (cm⁻¹) 3230, 2980-2760, 2370, 1465, 1430,1410, 1350-1020, 980, 920, 770-480.

This membrane was made of a copolymer composed essentially of repeatingunits of the formula (203) identified hereinafter. The ratio of p'/q'was about 7.6.

The amine-type polymer membrane thus obtained was immersed in a solutionof methyl iodide in dimethylformamide (volume ratio of 1/4) and reactedat 60° C. for 72 hours. The membrane thereby obtained was washed withmethanol and then reacted in a methanol solution of lithium chloride(concentration of 1.28M) at 60° C. for 24 hours. This membrane washeated to 60° C. in methanol, whereby a quaternary ammoniumchloride-type polymer membrane was obtained. In the dyeing test, themembrane thus obtained was not dyeable with Crystal Violet, and it wasdyed yellow (dark red in basic water) by Cresol Red, orange byBromothymol Blue and yellowish orange by Thymol Blue. Thus, the presenceof anion exchange groups was confirmed.

Infrared absorption spectrum (cm⁻¹) 3400, 3000-2930, 2830, 2360, 2120,1630, 1480, 1460, 1360-950, 930, 840, 780-480.

The absorption at 3400 and 1630 cm⁻¹ is considered to be attributable towater contained in the membrane.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (303) identified hereinafter. The ratioof p'/q' was about 7.6.

This anion exchange membrane had an ion exchange capacity of 0.72meq/g.dry membrane, an electric resistance of 5.4 Ωcm² and a transportnumber of 0.88. This membrane showed superior resistance to chlorinelike the membrane obtained in Example 1.

EXAMPLES 9 TO 12

A copolymer film [Nafion 125 (tradename) manufactured by Dupont Co.;thickness 125 μm; sulfonic acid-based ion exchange capacity: 0.83meq/g.dry film] obtained by the copolymerization of CF₂ =CF₂ with##STR59## was treated with 2N hydrochloric acid and then converted to asulfonyl chloride form, followed by hydrogen iodide treatment and alkaliwashing to convert it to a sodium carboxylate form. The pendant chainsof this membrane-form copolymer had a structure of ##STR60## Thismembrane was treated with a mixture of 8N hydrochloric acid/methanol(volume ratio of 1/1) for hydrolysis and esterification, and then heatedin a mixture of phosphorus pentachloride/phosphorus oxychloride (weightratio of 1/1.6) at 120° C. for 24 hours. Thereafter, it was washed incarbon tetrachloride and then dried. In the infrared absorptionspectrum, the membrane thereby obtained showed strong absorption at 1800cm⁻¹ attributable to carbonyl. Further, absorption was observed in thevicinity of 2980, 2880 and 1440 cm⁻¹, which is considered to beattributable to the absorption by C--H. Thus, it was found to be amixture-type polymer membrane wherein the terminal groups of the pendantchains were mostly --CO₂ Me groups and partly --COCl groups.

This mixture-type polymer membrane was composed substantially ofrepeating units of the formula (101) identified hereinafter, wherein Wis a methoxy group and a chlorine atom. The ratio of p'/q' was about7.6.

Membranes having various surface areas prepared in the above-mentionedmanner, were amidated in the same manner as in Example 8 by usingvarious amines as identified in Table 1, and then subjected to reductionand conversion to quaternary ammonium forms in the same manner as inExample 18. The structures and properties of the membranes therebyobtained are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                                     Main structures of copolymers                            Amidation            (p'/q' 42.6)                                      Surface areas  Reaction                                                                           Conversion          Quaternary                       Example                                                                            of the         time after reduction                                                                       Amide-type                                                                          Amine-type                                                                          ammonium-type                    Nos. membranes                                                                            Amines  (hr) (%)     membranes                                                                           membranes                                                                           membranes                        __________________________________________________________________________     9   16 cm.sup.2                                                                          Aniline 120  71      104   204   304                                          (5.4 ml)                                                          10    9 cm.sup.2                                                                          Propyl amine                                                                           44  77      105   205   305                                          (4.0 ml)                                                          11   16 cm.sup.2                                                                          Diethyl amine                                                                         120  60      106   206   306                                          (4.96 ml)                                                         12   18 cm.sup.2                                                                          Ammonia gas                                                                            25  61      107   207   301                                          (17.4 g)                                                          __________________________________________________________________________                 Final membranes                                                                          Ion exchange                                                                           Electric                                             Example                                                                            Dyeing     capacity resistance                                                                          Transport                                      Nos. tests*.sup.1                                                                             (meq/g. dry film)                                                                      (Ω cm.sup.2)                                                                  numbers                                                                             Durability                       __________________________________________________________________________             9   CV: Not dyeable                                                                          0.50     26.2  0.91  Same chlorine                                 CR: Yellow                      resistance as in                              TB: Orange                      Example 1                                10   CV: Not dyeable                                                                          0.61     12.5  0.90  Same chlorine                                 CR: Yellow                      resistance as in                              TB: Yellowish orange            Example 1                                     BTB: Orange                                                                   BTB(B): Dark blue                                                        11   CV: Not dyeable                                                                          0.46     33.8  0.91  Same chorine                                  CR: Yellow                      resistance as in                              TB: Orange                      Example 1                                12   CV: Not dyeable                                                                          0.48     28.1  0.91  Same chlorine                                 CR: Yellow                      resistance as in                              TB: Yellowish orange            Example 1                                     CR(B): Red                                                       __________________________________________________________________________     *.sup.1 CV . . . Crysial Violet                                               CR . . . Cresol Red                                                           TB . . . Thymol Blue                                                          BTB . . . Bromothymol Blue                                                    (B) . . . Basic                                                          

EXAMPLE 13

The same film (surface area: 8 cm²) as used as the starting material inExample 3, was treated in the same manner as in Example 1 to convert itto a sodium carboxylate form. This membrane was treated with a 3.24Nhydrochloric acid aqueous solution, then washed with water and driedunder reduced pressure to obtain a carboxylic acid-type polymermembrane. The resulting membrane was not dyeable with Crystal Violet.This membrane was immersed in 32 ml of acetonitrile and, after theaddition of 3.72 ml of triethylamine, 2.22 ml of n-propylamine and 3.54ml trimethylchlorosilane, heated under an argon atmosphere for 30minutes at room temperature and 73 hours at 80° C. The membrane wastaken out, washed with ether and dried under reduced pressure at 60° C.for 20 hours, whereby an amide-type polymer was obtained.

Infrared absorption spectrum (cm⁻¹) 3330, 3100, 2970, 2900, 2350, 1720,1530, 1440, 1390-1010, 980, 900-440.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (108)identified hereinafter. The ratio of p'/q' was about 6.5.

Under an argon atmosphere, the membrane thus obtained was immersed in550 ml of anhydrous tetrahydrofuran, and 9 g of sodium borohydride wasadded. Then, a solution of 18 ml of boron trifluoride in 15 ml oftetrahydrofuran was added dropwise in 40 minutes and stirred for 1.5hours under cooling with ice water. Then, the mixture was held at roomtemperature for 30 minutes and then refluxed for 21 hours. The membranewas taken out and washed in methanol under reflux for 21 hours. Themembrane was taken out and dried under reduced pressure at 60° C. for 20hours, whereby an amine-type polymer membrane was obtained. In theinfrared absorption spectrum of this membrane, the absorption at 1720cm⁻¹ attributable to amide carbonyl disappeared, thus indicating thatthe reduction to the amine-type membrane proceeded completely. Thismembrane was not dyeable with Crystal Violet, but it was dyed yellow byBromothymol Blue.

Infrared absorption spectrum (cm⁻¹) 3600-3100, 2950, 2900, 2370, 1460,1420-900, 900-440.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (208)identified hereinafter. The ratio of p'/q' was about 6.5.

The membrane thus obtained was immersed in a solution of 60 ml of methyliodide in 240 ml of dimethylformamide, and heated at 60° C. for 72hours, whereby an ammonium iodide-type polymer membrane was obtained.

Then, this membrane was immersed in 300 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 25 hours (the solution wasreplaced at an intermediate point during the operation). Then, themembrane was washed in methanol at 60° C. for 30 hours, whereby anammonium chloride-type polymer membrane was obtained.

This membrane was not dyeable with Crystal Violet, but it was dyedyellow (dark red in basic water) with Cresol Red and orange (blue inbasic water) with Bromothymol Blue. Thus, the membrane was found to haveion exchange groups.

Infrared absorption spectrum (cm⁻¹) 3400-2800, 2360, 1460-1410,1350-940, 840-480.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (305)identified hereinafter. The ratio of p'/q' was about 6.5.

The membrane thus obtained had an electric resistance of 10.0 Ωcm² and atransport number of 0.90. This membrane also exhibited superiordurability.

EXAMPLE 14

A part of the amine-type polymer membrane obtained in the first part ofthe operation of Example 1, was immersed in a solution of 2 ml of ehtyliodide in 8 ml of methanol and heated at 60° C. for 72 hours, whereby anammonium iodide-type polymer membrane was obtained. This membrane wasmade of a copolymer composed substantially of repeating units of theformula (307) identified hereinafter. The ratio of p'/q' was about 6.5.This membrane was immersed in a 10% methanol solution of lithiumchloride, and heated at 60° C. for 25 hours (the solution was replacedat an intermediate point during the operation). Then, the membrane waswashed in methanol at 60° C. for 18 hours, whereby an ammonium chloridetype polymer was obtained. This membrane had a structure substantiallysimilar to the formula (307) wherein the iodine ion was replaced by achlorine ion.

This membrane was not dyeable with Crystal Violet, but it was dyedyellow with Cresol Red and blue with basic Bromothymol Blue.

The membrane thus obtained had an ion exchange capacity of 0.82meq/g.dry membrane, an electric resistance of 5.6 Ωcm² and a transportnumber of 0.88. This membrane showed superior resistance to chlorinelike the membrane obtained in Example 1.

Infrared absorption spectrum (cm⁻¹) 3400, 3040, 2970, 2850, 2830, 2800,2360, 1630, 1480, 1420, 1340-1060, 980, 930, 840, 740-500.

The absorption at 3400 and 1630 cm⁻¹ is considered to be attributable towater in the membrane.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (308).

The ratio of p'/q' was about 6.5.

EXAMPLE 15

The same membrane as used in Examples 9 to 12 was treated in the samemanner as in those Examples to convert it to a sodium carboxylate-typemembrane. This membrane was treated with a 3.24N hydrochloric acidaqueous solution, then washed with water and dried under reducedpressure to obtain a carboxylic acid-type polymer membrane. In theinfrared absorption spectrum, this membrane showed strong absorption bycarbonyl at 1780 cm⁻¹. Further, it was dyed blue with Crystal Violet.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (1) identified hereinafter, wherein W wasa hydroxyl group. The ratio of p'/q' was about 7.6.

The carboxylic acid-type polymer membrane (9 cm²) thus obtained wasimmersed in 32 ml of anhydrous acetonitrile and, after the addition of3.72 ml of triethyl amine, 1.62 ml of ethanol amine and 7.1 ml oftrimethylchlorosilane, heated under an argon atmosphere at 80° C. for 76hours. The membrane was taken out, washed with methanol and dried underreduced pressure at 60° C. for 24 hours, whereby an amide-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3340, 3100, 2950, 2350, 1720, 1535,1430, 1350-930, 880-480.

This membrane was made of a copolymer composed essentially of repeatingunits of the formula (109) identified hereinafter. The ratio of p'/q'was about 7.6.

Under an argon atmosphere, the membrane thus obtained was immersed in170 ml of anhydrous tetrahydrofuran, and 3 g of sodium borohydride wasadded thereto. Then, a solution of 6 ml of boron trifluoride ethyl ethercomplex in 10 ml of tetrahydrofuran was added dropwise in 30 minutesunder cooling with ice water and stirred for 1.5 hours. Then, thesolution was held at room temperature for 30 minutes and further heatedfor 20 hours under reflux. The membrane was taken out and dried underreduced pressure at 60° C. for 24 hours, whereby an amine-type polymermembrane was obtained. In the infrared absorption spectrum of thismembrane, the absorption at 1720 cm⁻¹ attributable to amide carbonyldisappeared, thus indicating that the reduction to the amine-typemembrane proceeded completely. The conversion as calculated from thevalues obtained by the elementary analysis, was about 82%. This membranewas not dyeable with Crystal Violet, basic Cresol Red, basic BromothymolBlue or basic Thymol Blue, but it was dyed yellow by Cresol Red, orangeby Thymol Blue and yellowish orange by Bromothymol Blue.

Infrared absorption spectrum (cm⁻¹) 3550-3175, 3000-2820, 2350, 1440,1360-950, 860-500.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (209) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 25 ml of methyliodide in 100 ml of dimethylformamide, and heated at 60° C. for 120hours, whereby an ammonium iodide-type polymer membrane was obtained.Then, this membrane was immersed in 125 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 24 horus (the solution wasreplaced at an intermediate point during the operation). Then, themembrane was washed in methanol at 60° C. for 7.5 hours, whereby anammonium chloride-type polymer membrane was obtained. This membrane wasnot dyeable with Crystal Violet, but it was dyed clear yellow by CresolRed, orange by Thymol Blue, black by Bromothymol Blue, light blue bybasic Bromothymol Blue and dark red by basic Cresol Red.

Infrared absorption spectrum (cm⁻¹) 3600-3125, 3000, 2350, 1630, 1480,1350-940, 850-500.

The membrane thus obtained had an ion exchange capacity of 0.70meq/g.dry membrane, an electric resistance of 11.9 Ωcm² and a transportnumber of 0.90.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (309) identified hereinafter. The ratioof p'/q' was about 7.6.

This membrane showed superior chemical resistance and solventresistance.

EXAMPLE 16

Under an argon atmosphere, a carboxylic acid-type polymer membrane (42cm²) obtained in the same manner as in Example 15, was immersed in 150ml of anhydrous dimethoxyethane and, after the addition of 18.6 ml (135mmol) of triethylamine, 15 ml (135 mmol) of N-methylpiperazine and 17.8ml (140 mmol) of trimethylchlorosilane, heated and stirred at 90° C. for66 hours. The membrane was taken out, washed with methanol and driedunder reduced pressure at 60° C. for 24 hours, whereby light brownopaque amido-type polymer membrane was obtained. In the infraredabsorption spectrum of this membrane, the absorption at 1780 cm⁻¹attributable to a carboxylic acid disappeared, and the absorption by C-Hwas observed at 3000-2800 and 1450 cm⁻¹ and strong absorptionattributable to amide carbonyl was observed at 1700 cm⁻¹. This membranewas made of a copolymer composed substantially of repeating units of theformula (110) identified hereinafter. The ratio of p'/q' was about 7.6.

The amide-type membrane thus obtained was immersed in 275 ml ofanhydrous tetrahydrofuan, and 7.5 g of sodium borohydride was added.Then, a solution of 15 ml of a boron trifluoride ethyl ether complex in25 ml of tetrahydrofuran was dropwise added in 30 minutes under coolingwith ice and stirred for 1.5 hours. The solution was stirred for 30minutes at room temperature and further heated for 17 hours underreflux. The membrane was taken out, washed in methanol under reflux for20 hours, and dried under reduced pressure at 60° C. for 24 hours,whereby an amine-type polymer membrane was obtained. From the valuesobtained by the elementary analysis of the membrane, the conversion wasfound to be about 87%. This membrane was made of a copolymer composedsubstantially of the formula (210) identified hereinafter. The ratio ofp'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of methanol and heated at 60° C. for 72 hours, wherebyquaternary ammonium salt-type polymer membrane was obtained. Thismembrane was made of a copolymer composed substantially of repeatingunits of the formula (310) identified hereinafter. The ratio of p'/q'was made about 7.6. Then, this membrane was immersed in 250 ml of a 10%methanol solution of lithium chloride and heated at 60° C. for 24 hours(the solution was replaced at an intermediate point during theoperation). Then, the membrane was washed in methanol at 60° C. for 7hours, whereby an ammonium chloride-type polymer membrane wherein theiodine ion was replaced by a chlorine ion (i.e. a copolymer membranecomposed substantially of repeating units of the formula (311)identified hereinafter) was obtained. This membrane was not dyeable withCrystal Violet, but it was dyed yellow by Cresol Red, dark red by basicCresol Red and dark blue by basic Thymol Blue.

Infrared absorption spectrum (cm⁻¹) 3400, 3030, 2950, 2870, 2370, 1630,1460-1485, 1380-1030, 1020-910, 870-460.

The membrane thus obtained had an ion exchange capacity of 0.71meq/g.dry membrane, an electric resistance of 10.5 Ωcm² and a transportnumber of 0.88. This membrane exhibited superior durability particularlyunder a strong basic condition. For instance, even when heated inethylenediamine in the presence of ethylenediamine hydrochloride, at 50°C. for 100 hours, no change was observed in the above values. Whereas, acommercially available hydrocarbon-type anion exchange membraneimmediately turned black under the above condition, whereupon themembrane was destroyed.

EXAMPLE 17

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 13, was immersed in 170 ml of anhydrousdimethoxyethane and, after the addition of 12.4 ml of triethylamine, 10ml of N-methylpiperazine and 11.4 ml of trimethylchlorosilane, heatedunder an argon atmosphere at 90° C. for 68 hours. The membrane was takenout, washed with ether and dried under reduced pressure at 60° C. for 27hours, whereby an amide-type polymer membrane was obtained.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (110)identified hereinafter. The ratio of p'/q' was about 6.5.

Under an argon atmosphere, the amide-type polymer membrane thusobtained, was immersed in 300 ml of anhydrous tetrahydrofuran, and 4.5 gof sodium borohydride was added thereto. Then, 9 ml of a borontrifluoride ethyl ether complex was added dropwise in 35 minutes undercooling with ice water and stirred for 1.5 hours. Then, the solution wasstirred at room temeprature for 30 minutes and further refluxed underheating for 17 hours. After cooling, the membrane was taken out andwashed with methanol under reflux for 22 hours, whereby an amine-typepolymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 2950, 2800, 2380, 1440, 1380-900,880-460.

The absorption in the vicinity of 1700 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely. This membrane was not dyeablewith Crystal Violet or basic Thymol Blue, but it was dyed yellow byCresol Red and orange by Thymol Blue.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (210)identified hereinafter. The ratio of p'/q' was about 6.5.

The amine-type polymer membrane thus obtained, was immersed in 200 ml ofmethanol and, after the addition of 50 ml of methyl iodide, heated at60° C. for 48 hours. The membrane was taken out, then immersed in 250 mlof a 10% methanol solution of lithium chloride and heated at 60° C. for24 hours (the solution was replaced at an intermediate point of thisoperation). The membrane was taken out and washed with methanol at 60°C. for 8 hours, whereby an ammonium chloride-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3600-3100, 3050-2750, 2350, 1620,1500-1380, 1370-890, 880-400.

This membrane was not dyeable with Crystal Violet, but it was dyedyellow by Cresol Red and dark blue by basic Thymol Blue.

The membrane thus obtained had an electric resistance of 12 Ωcm² andtransport number of 0.89. This membrane showed superior resistance tobase like the membrane obtained in Example 16.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (311)identified hereinafter. The ratio of p'/q' was about 6.5.

EXAMPLE 18

A carboxylic acid-type membrane similar to the one used in Example 4,was converted to an acid chloride-type membrane in the same manner as inExample 4. The acid chloride-type membrane was immersed in a dried ethersolution of N-methylpiperazine, and allowed to stand at room temperaturefor 64 hours. Then, it was heated in a 1% sodium bicarbonate aqueoussolution at 80° C. for 6 hours and then dried under vacuum at 50° C.,whereby a colorless membrane was obtained. The membrane was not dyeablewith Crystal Violet. In the infrared spectrum, the absorption at 1800cm⁻¹ disappeared, and strong absorption was observed anew at 1690 cm⁻¹,which is considered to be attributable to carbonyl in the carboxylicacid amide.

The membrane thus obtained was then immersed in a dried diethyleneglycol dimethyl ether solution of sodium borohydride, and under an argonatmosphere, a dried diethylene glycol dimethyl ether solution of a borontrifluoride ether complex was dropwise added under cooling with ice. Thereaction was conducted for 5 hours under cooling and for further 18hours at 100° C., whereby the reduction proceeded completely.

The diamine-type membrane thus obtained, was washed with methanol, andreacted with methyl iodide in methanol at 0° C. for 2 days. Further, themembrane was washed with methanol, and then treated with a methanolsolution of lithium chloride at 0° C. for 2 days, whereby it was againwashed with methanol under heating to obtain an anion exchange membranehaving quaternary ammonium chloride groups. In the infrared spectrum,the membrane thus obtained showed an absorption at 3030, 2950, 2870,1485, 980 and 940 cm⁻¹. The membrane was homogeneously dyed byBromocresol Purple or Cresol Red. Thus, the presence of anion exchangegroups was confirmed. This membrane was made of a copolymer composedsubstantially of repeating units of the formula (311) identifiedhereinafter. The membrane had an ion exchange capacity of 0.85 meq/g.drymembrane (no change of the equivalent weight was taken into account), anelectric resistance of 3.9 Ωcm² and a transport number of 0.84. Thismembrane showed superior durability particularly under a strong basiccondition. For instance, no change was observed in the above-mentionedvalues, even when it was heated in ethylenediamine at 50° C. for 100hours. Whereas, a commercially available hydrocarbon-type anion exchangemembrane immediately turned black under this condition, and the membranewas destroyed.

EXAMPLE 19

The same film as used as the starting material in Example 2, wasimmersed in a tetrahydrofuran solution of N-methylpiperazine and reactedunder reflux for 24 hours. Then, it was treated in a 1% sodiumbicarbonate aqueous solution at 80° C. for 5 hours and then dried undervacuum at 50° C.

The infrared spectrum of the membrane thus obtained was substantiallythe same as the spectrum of the aminecarboxylic amide-type membraneobtained in Example 18.

The aminocarboxylic acid amide-type membrane was subjected to thereduction, the alkylation by means of methyl iodide and the counter ionexchange by means of lithium chloride in the same manner as in Example18, whereby an anion exchange membrane having the desired quaternaryammonium chloride groups was obtained. The infrared spectrum of themembrane thus obtained, was substantially the same as the spectrum ofthe membrane obtained in Example 18. Further, the membrane had similardyeability. This membrane was made of a copolymer composed substantiallyof repeating units of the formula (312) identified hereinafter. Themembrane had an ion exchange capacity of 1.3 meq/g.dry membrane (nochange of the equivalent weight was taken into account), an electricresistance of 3.0 Ωcm² and a transport number of 0.86. This membraneshowed superior resistance to base like the membrane obtained in Example18.

EXAMPLE 20

A tubular carboxylic acid-type membrane similar to the one used inExample 6 was converted to a tubular acid chloride-type membrane in thesame manner as in Example 4. The tubular acid chloride-type membrane wasimmersed in a dried ether solution of N-methylpiperazine and allowed tostand at room temperature for 64 hours. The membrane was heated in a 1%sodium bicarbonate aqueous solution at 80° C. for 6 hours, and thendried under vacuum at 50° C., whereby a colorless tubular membrane wasobtained. The tubular membrane was not dyed by Crystal Violet.

The tubular membrane thus obtained was immersed in a dried diethyleneglycol dimethyl ether solution of sodium borohydride, and under an argonatmosphere, a dried diethylene glycol dimethyl ether solution of borontrifluoride ether complex was dropwise added thereto under cooling withice. The reaction was conducted for 5 hours under cooling and further 18hours at 100° C., whereby the reduction proceeded completely.

The tubular diamine-type membrane thus obtained, was washed withmethanol and then reacted with methyl iodide in methanol at 0° C. for 2days. Further, it was washed with methanol and then reacted in amethanol solution of lithium chloride at 0° C. for 2 days, whereupon itwas washed again with methanol under heating to obtain a tubular anionexchange membrane having the desired quaternary ammonium chloridegroups. This membrane was homogeneously dyed by Bromocresol Purple andCresol Red. Thus, the presence of anion exchange groups was confirmed.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (311) identified hereinafter. The ratioof p'/q' was about 6.4. The tubular anion exchange membrane had an ionexchange capacity of 0.80 meq/g.dry resin (no change of the equivalentweight was taken into account).

EXAMPLE 21

A carboxylic acid-type polymer membrane (3.6 cm²) obtained in the samemanner as in Example 15, was immersed in 10 ml of n-butyl alcohol and,after allowing it to absorb 1.73 g of hydrogen chloride at roomtemperature, heated at 65° C. for 65 hours. The membrane was taken outand dried under reduced pressure at 60° C. for 24 hours, whereby an-butyl ester-type polymer membrane was obtained. This membrane showedstrong absorption by carbonyl at 1790 cm⁻¹. Further, this membrane wasnot dyeable with Crystal Violet.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (1) identified hereinafter, wherein W wasa n-butoxy group. The ratio of p'/q' was about 7.6.

The n-butylester-type polymer membrane (1.7 cm²) thus obtained wasimmersed in 15 ml of anhydrous tetrahydrofuran, and 0.5 ml ofN,N,N'-trimethylethylenediamine was added thereto. Under an argonatmosphere, the mixture was refluxed 74 hours. The membrane was takenout and dried under reduced pressure at 60° C. for 20 hours, whereby alight brown opaque amide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3400, 2970, 2880, 2850, 2800, 2400,1700, 1460, 1420, 1370-1020, 980, 940, 850, 820-480.

The absorption at 1790 cm⁻¹ attributable to the ester diappeared.Absorption by C-H was observed at 3000-2800 and 1460 cm⁻¹, and strongabsorption attributable to amide carbonyl was observed at 1700 cm⁻¹.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (111) identified hereinafter. The ratioof p'/q' was about 7.6.

The amide-type membrane thus obtained was reduced in the same manner asin Example 16, whereby a colorless transparent amine-type polymer wasobtained. In the infrared absorption spectrum of this membrane, theabsorption at 1700 cm⁻¹ attributable to amide carbonyl disappeared, thusindicating that the reduction to the amine-type membrane proceededcompletely. The conversion from the ester was calculated from the valuesobtained by the elementary analysis and was found to be about 70%. Thismembrane was not dyeable with Crystal Violet or basic Thymol Blue, butit was dyed yellow by Cresol Red and orange by Thymol Blue.

Infrared absorption spectrum (cm⁻¹) 3000-2800, 2380, 1460, 1380-920,880-460.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (211) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 22

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 15, was immersed in 160 ml of anhydrousdimethoxyethane and, after the addition of 14 ml of triethylamine, 11.3ml of N,N,N'-trimethylethylenediamine and 13.3 ml oftrimethyhlchlorosilane, heated under an argon atmosphere at 90° C. for66 hours, whereby an amide-type polymer membrane was obtained.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (111) identified hereinafter. The ratioof p'/q' was about 7.6.

This amide-type polymer membrane was reduced in the same manner as inExample 16, whereby an amine-type polymer membrane was obtained. Theconversion was about 91%. The infrared absorption spectrum and thedyeability of the membrane thus obtained were substantially the same asthose obtained in Example 21.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (211) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of methanol and heated at 60° C. for 48 hours, wherebyan ammonium iodide-type polymer membrane was obtained.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (313) identified hereinafter. The ratioof p'/q' was about 7.6.

This membrane was immersed in 250 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 24 hours (the solution wasrenewed at an intermediate point during the operation). Then, themembrane was immersed in methanol and washed therein at 60° C. for 8hours, whereby an ammonium chloride-type polymer membrane was obtained.This membrane was not dyeable with Crystal Violet, but it was dyedyellow by Cresol Red and blue by basic Thymol Blue.

The membrane thus obtained had an ion exchange capacity of 0.73meq/g.dry membrane, an electric resistance of 6.5 Ωcm² and a transportnumber of 0.87. This membrane showed superior resistance to base likethe membrane obtained in Example 16.

Infrared absorption spectrum (cm⁻¹) 3400, 3000, 2950, 2370, 1630, 1470,1360-1020, 1010-910, 860, 840-480.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (314) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 23

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 13, was immersed in 165 ml of anhydrousdimethoxyethane and, after the addition of 9.3 ml of triethylamine, 7.5ml of N,N,N'-trimethylethylenediamine and 8.55 ml oftrimethyhlchlorosilane, heated under an argon atmosphere at 90° C. for48 hours. The membrane was taken out, washed with ether and dried underreduced pressure at 60° C. for 24 hours, whereby an amide-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3400, 2950, 2780, 1670, 1440,1370-900, 880-400.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (111)identified hereinafter. The ratio of p'/q' was about 6.5.

The membrane thus obtained was reduced in the same manner as in Example17, whereby an amine-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3050-2700, 2370, 1430, 1380-900,860-400.

The absorption in the vicinity of 1700 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely. This membrane was not dyeablewith Crystal Violet and basic Thymol Blue, but it was dyed yellow byCresol Red and orange by Thymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (211) identified hereinafter. The ratioof p'/q' was about 6.5.

The amine-type polymer membrane thus obtained was treated in the samemanner as in Example 22, whereby an ammonium chloride-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3650-3100, 3100-2700, 2350, 1620,1510-1380, 1370-900, 880-400.

The dyeability of this membrane was the same as in Example 21.

The membrane thus obtained had an electric resistance of 7.7 Ωcm² and atransport number of 0.87. This membrane showed superior resistance tobase like the membrane obtained in Example 16.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (314)identified hereinafter. The ratio of p'/q' was about 6.5.

EXAMPLE 24

A copolymer obtained by the copolymerization of ##STR61## was formedinto a membrane (thickness: 50 μm; SO₃ H-based ion exchange capacity:0.95 meq/g.dry membrane) and then saponified to obtain a sodiumsalt-type membrane. This membrane was further treated with concentratedhydrochloric acid/methanol (3/1) and then subjected to heat treatment in3.24N hydrochloric acid. Then, the membrane was taken out, washed withwater and dried under reduced pressure to obtain a carboxylic acid-typemembrane. This membrane was made of a copolymer composed substantiallyof repeating units of the formula (2) identified hereinafter, wherein Wwas a hydroxyl group. The ratio of p'/q' was about 6.4.

The carboxylic acid-type membrane (42 cm²) thus obtained was immersed in160 ml of anhydrous dimethoxyethane and, after the addition of 9.3 ml oftriethylamine, 7.5 ml of N,N,N'-trimethylethylenediamine and 8.55 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 72hours. The membrane was taken out and dried under reduced pressure at60° C. for 24 hours, whereby an amido-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3400, 2960, 2840, 2780, 2450, 1680,1470, 1415, 1360-1080, 1010, 975, 845, 800, 630.

This membrane was made of the copolymer composed substantially ofrepeating units of the formula (112) identified hereinafter. The ratioof p'/q' was about 6.4.

The amide-type polymer membrane thus obtained, was then reduced in thesame manner as in Example 17, whereby an amine-type polymer membrane wasobtained (conversion: 88%).

Infrared absorption spectrum (cm⁻¹) 3150, 2970, 2880, 2830, 2800, 2390,1465, 1380-990, 980, 810, 770, 630.

The absorption in the vicinity of 1680 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely.

The membrane was made of a copolymer composed substantially of repeatingunits of the formula (212) identified hereinafter. The ratio of p'/q'was about 6.4.

The amine-type polymer membrane thus obtained was treated in the samemanner as in Example 22, whereby an ammonium chloride-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3650-3100, 3030, 2970, 2870, 2350,1630, 1485, 1380-1060, 1010, 980, 920, 865, 810, 630.

The dyeability of this membrane was the same as the membrane obtained inExample 21. The membrane had an ion exchange capacity of 0.74 meq/g.drymembrane, an electric resistance of 2.2 Ωcm² and a transport number of0.85. This membrane showed superior resistance to base like the membraneobtained in Example 16.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (315) identified hereinafter. The ratioof p'/q' was about 6.4.

EXAMPLE 25

A methyl ester-type membrane similar to the one used in Example 4, wasimmersed in the dry ether solution of N,N,N'-trimethylethylenediamineand reacted at room temeprature for 20 hours. The membrane was washedwith ether and dried under reduced pressure, whereby a colorlessmembrane was obtained. In the infrared spectrum, absorption by C--H wasobserved at 3000, 2925 and 2850 cm⁻¹, and absorption by carbonyl wasobserved at 1700 cm⁻¹. This membrane was not dyeable with CrystalViolet. This membrane was subjected to the same operation (reduction,alkylation and counter ion exchange) as in Example 4, whereby aquaternary ammonium chloride-type anion exchange membrane was obtained.The membrane thus obtained showed infrared absorption by C--H at3000-2900 cm⁻¹ and it was homogeneously dyed by Cresol Red. Thismembrane was made of a copolymer composed substantially of repeatingunits of the formula (313) identified hereinafter. The ratio of p'/q'was about 6.4.

The membrane had an ion exchange capacity of 1.2 meq/g.dry membrane (nochange of the equivalent weight was taken into account), an electricresistance of 3.5 Ωcm² and a transport number of 0.86. The resistance tobase was substantially the same as in Example 18.

EXAMPLE 26

The same copolymer as used as the starting material in Example 6, wasformed into a tube in the same manner as in Example 6, then saponified.The tubular membrane was further treated with 2N hydrochloric acid inaccordance with the conventional method, then converted to a sulfonylchloride-form, and then subjected to hydrogen iodide treatment, followedby washing with alkali, whereby a sodium carboxylate-type membrane wasobtained. This membrane was treated with 3.24N hydrochloric aqueoussolution, then washed with water and dried under reduced pressure,whereby a tubular carboxylic acid-type copolymer was obtained. Thiscopolymer was composed substantially of repeating units of the formula(1) identified hereinafter, wherein W was a hydroxyl group. The ratio ofp'/q' was about 6.4.

The tubular carboxylic acid-type polymer (50 cm) thus obtained wasimmersed in 165 ml of anhydrous dimethoxyethane to fill the tube withthe solvent and, after the addition of 9.3 ml of triethylamine, 7.5 mlof N,N,N'-trimethylethylenediamine and 8.55 ml of trimethylchlorosilane,heated under an argon atmosphere at 90° C. for 48 hours, whereby anamide-type polymer was obtained. The infrared absorption spectrum of thetubular amide-type polymer was substantially the same as the spectrum ofthe amide-type polymer membrane obtained in Example 21. The conversionwas 83%. The tubular polymer thus obtained was cut into rings andsubjected to dyeability test. The polymer was not dyeable with CrystalViolet.

The tubular amide-type polymer was composed substantially of repeatingunits of the formula (111) identified hereinafter. The ratio of p'/q'was about 6.4.

The tubular amide-type polymer thus obtained was immersed in a driedethylene glycol dimethyl ether under an argon atmosphere, so that insideof the tube was filled with diethylene glycol dimethyl ether. Then,sodium borohydride was added to a concentration of 0.53 mol, thoroughlymixed and then cooled, whereupon a dried diethylene glycol dimethylether solution of a boron trifluoride ether complex (0.62 mol per mol ofsodium borohydride), was dropwise added under cooling with ice. Thereaction was conducted for 2.5 hours under cooling and further 21 hoursat 100° C. The tubular amine-type polymer thus obtained, was washed withmethanol, then dried and examined for the infrared absorption spectrum.The infrared absorption spectrum was substantially the same as thespectrum of the amine-type polymer membrane obtained in Example 21. Theconversion was 78%. The tubular polymer thus obtained was cut into ringsand tested for the dyeability. The dyeability was substantially the sameas the amine-type polymer membrane obtained in Example 21.

This amine-type polymer was composed substantially of repeating units ofthe formula (211) identified hereinafter. The ratio of p'/q' was about6.4.

The tubular amine-type polymer was immersed in a solution of methyliodide in methanol (volume ratio of 1/4) and reacted at 60° C. for 50hours. The tubular polymer thereby obtained, was washed with methanoland then reacted in a methanol solution of lithium chloride(concentration of 1.28M). This tubular polymer was heated in methanol to60° C., whereby a tubular ammonium chloride-type polymer was obtained.The tubular polymer thus obtained, was not dyeable with Crystal Violet,but it was dyed dark blue by basic Thymol Blue and yellow by Cresol Red.Thus, the presence of anion exchange groups was confirmed.

The tubular anion exchanger thus obtained had an ion exchange capacityof 0.69 meq/g.dry resin. No change was observed in the value even whenthe anion exchanger was treated in methanol at 65° C. for 48 hours,followed by the removal of the solvent under vacuum at 40° C., and thisoperation was repeated 5 times.

This tube was made of a copolymer composed substantially of repeatingunits of the formula (314) identified hereinafter. The ratio of p'/q'was about 6.4.

EXAMPLE 27

The same copolymer powder as used as the starting material in Example 7,was treated in the same manner as in Example 7 to convert it to asulfonyl chloride-form. Then, the powder was subjected to hydrogeniodide treatment and washing with alkali to convert it to a sodiumcarboxylate-form. Thereafter, the powder was treated with 3.24Nhydrochloric acid, then washed with water and dried under reducedpressure, whereby a powder carboxylic acid-type polymer was obtained.This powder polymer was formed into a KBr disc and examined for theinfrared absorption spectrum. The polymer showed absorption by carbonylin the vicinity of 1780 cm⁻¹, and it was dyed blue by Crystal Violet.

This powder was made of a copolymer composed substantially of repeatingunits of the formula (1) identified hereinafter, wherein W was ahydroxyl group. The ratio of p'/q' was about 6.6.

The powder carboxylic acid-type polymer (1.0 g) thus obtained, wasimmersed in 165 ml of anhydrous dimethoxyethane and, after the additionof 9.3 ml of triethylamine, 7.5 ml of N,N,N'-trimethylethylenediamineand 8.55 ml of trimethylchlorosilane, heated under an argon atmosphereat 90° C. for 48 hours, whereby an amide-type polymer was obtained.

The powder thereby obtained was formed into a KBr disc and examined forthe infrared absorption spectrum. Absorption attributable to amidecarbonyl was observed at about 1700 cm⁻¹. The conversion was 76%. Thepowder polymer thus obtained, was not dyed by Crystal Violet at all.

The amide-type polymer constituting this powder, was composedsubstantially of repeating units of the formula (111) identifiedhereinafter. The ratio of p'/q' was about 6.6.

The powder amide-type polymer thus obtained, was immersed in 55 ml ofanhydrous tetrahydrofuran under an argon atmosphere, and 1.5 g of sodiumborohydride was added. Then, a solution of 3 ml of boron trifluorideethyl ether complex in 5 ml of tetrahydrofuran was dropwise added in 30minutes under cooling with ice water and stirred for 1.5 hours.Thereafter, the mixture was stirred at room temperature for 30 minutesand then refluxed under heating for 17 hours. The polymer powder wasseparated and washed in methanol under reflux for 20 hours. Aftercooling, the mixture was filtered to collect a powder amine-typepolymer. The conversion was 74%. The powder thus obtained was formedinto a KBr disc and examined for the infrared absorption spectrum. Theabsorption at about 1700 cm⁻¹ attributable to amide carbonyl disappearedcompletely.

This powder was not dyeable with Crystal Violet or basic Thymol Blue,but it was dyed yellow with Cresol Red and orange by Thymol Blue.

This amine-type polymer was composed substantially of repeating units ofthe formula (211) identified hereinafter. The ratio of p'/q' was about6.6.

The powder amine-type polymer thus obtained was subjected to conversionto a quaternary ammonium form and counter ion exchange in the samemanner as in Example 7, whereby a desired powder ammonium chloride-typepolymer was obtained. The powder polymer thus obtained was not dyeablewith Crystal Violet, but it was dyed dark blue by basic Thymol Blue andyellow by Cresol Red. Thus, the presence of anion exchange groups wasconfirmed.

The powder anion exchanger thus obtained, had a ion exchange capacity of0.64 meq/g.dry resin. No change was observed in the value even when theanion exchanger was treated in methanol at 65° C. for 48 hours, followedby the removal of the solvent under vacuum at 40° C., and this operationwas repeated 5 times.

This powder was made of a copolymer composed substantially of repeatingunits of the formula (314) identified hereinafter. The ratio of p'/q'was about 6.6.

EXAMPLE 28

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 13, was immersed in 150 ml of anhydrousacetonitrile and, after the addition of 16.43 ml of triethylamine, 13.1ml of N,N-dimethylethylenediamine and 15.8 ml of trimethylchlorosilane,heated under an argon atmosphere at room temperature for 30 minutes andfurther at 80° C. for 70 hours. The membrane was taken out, washed withether and dried under reduced pressure at 60° C. for 20 hours, wherebyan amide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3320, 2930, 2800, 2350, 1710,1580-1410, 1400-900, 900-440.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (113)identified hereinafter. The ratio of p'/q' was about 6.5.

Under an argon atmosphere, the membrane thus obtained, was immersed in450 ml of anhydrous tetrahydrofuran, and 8 g of sodium borohydride wasadded. Then, a solution of 16 ml of boron trifluoride ethyl ethercomplex in 15 ml of tetrahydrofuran, was added dropwise in 40 minutesunder cooling with ice water and stirred for 1.2 hours. Then, themixture was stirred at room temperature for 30 minutes and refluxedunder heating for 19 hours. The membrane was taken out, washed inmethanol under reflux for 22 hours and then dried under reduced pressureat 60° C. for 24 hours, whereby an amine-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3360, 3000-2700, 2350, 1450,1400-900, 880-440

The absorption at 1710 cm⁻¹ attributable to amide carbonyl disappeared,thus indicating that the reduction to the amine-type membrane proceededcompletely.

This membrane was dyed orange by Cresol Red, yellowish orange by ThymolBlue and blackish green by Bromothymol Blue, and it was not dyeableunder the respective basic conditions.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (213)identified hereinafter. The ratio of p'/q' was about 6.5.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of methanol and heated at 60° C. for 72 hours, wherebyan ammonium iodide-type polymer membrane was obtained. Then, thismembrane was immersed in 250 ml of a methanol solution containing 10% oflithium chloride and heated at 60° C. for 24 hours (the solution wasreplaced at an intermediate point during the operation).

Thereafter, the membrane was washed in methanol at 60° C. for 8 hours,whereby an ammonium chloride-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3700-3100, 3050-2750, 2350, 1620,1510-1380, 1370-880, 870-440.

This membrane was dyed yellow by Cresol Red, red by basic Cresol Red,yellowish orange by Thymol Blue, bluish green by basic Thymol Blue, darkorange by Bromothymol Blue and black by basic Bromothymol Blue.

The membrane had an electric resistance of 9 Ωcm² and a transport numberof 0.88. This membrane showed superior resistance to base like themembrane obtained in Example 16.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (314)identified hereinafter. The ratio of p'/q' was about 6.5.

EXAMPLE 29

A carboxylic acid-type polymer membrane (14 cm²) obtained in the samemanner as in Example 15, was mixed with 3.4 ml of1-(2-aminoethyl)pyrrolidine, 32 ml of anhdyrous acetonitrile, 3.7 ml oftrimethylamine and 3.5 ml of trimethylchlorosilane, and heated under anargon atmosphere at 80° C. for 96 hours. The membrane was taken out,washed with ether and then dried under reduced pressure at 60° C. for 22hours, whereby an amide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3350, 3000-2770, 2350, 1720, 1530,1440, 1360-1020, 980, 840, 795-480.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (114) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was immersed in 170 ml of anhydroustetrahydrofuran under an argon atmosphere, and 3.0 g of sodiumborohydride was added. Then, a solution of 6 ml of boron trifluorideethyl ether complex in 10 ml of tetrahydrofuran, was added dropwise in30 minutes under cooling with ice water and stirred for 1.5 hours. Then,the mixture was stirred at room temperature for 30 minutes and furtherrefluxed under heating for 20 hours. The membrane was taken out andwashed in methanol under reflux for 20 hours. The membrane was taken outand dried under reduced pressure at 60° C. for 24 hours, whereby anamine-type polymer membrane was obtained. In the infrared absorptionspectrum of this membrane, the absorption at 1720 cm⁻¹ attributable toamide carbonyl disappeared, thus indicating that the reduction to theamine-type membrane proceeded completely. The conversion was about 91%.This membrane was not dyeable with Crystal Violet, basic Thymol Blue orbasic Bromothymol Blue, but it was dyed yellow by Cresol Red, lightyellow by basic Cresol Red, orange by Thumol Blue and dark blue byBromothymol Blue.

Infrared absorption spectrum (cm⁻¹) 3350, 2920, 2800, 2350, 1460,1350-950, 860-485.

This membrane was made of a copolymer composed subantially of repeatingunits of the formula (214) identified hereinafter. The ratio of p'/q'was about 7.6. The membrane thus obtained was immersed in a solution of20 ml of methyl iodide in 80 ml of methanol and heated at 60° C. for 72hours, whereby an ammonium iodide-type polymer membrane was obtained.Then, this membrane was immersed in 100 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 20 hours (the solution wasreplaced at an intermediate point of this operation). Thereafter, themembrane was immersed in methanol and washed at 60° C. for 8 hours,whereby an ammonium chloride-type polymer membrane was obtained. Thismembrane was not dyeable with Crystal Violet, but it was dyed clearyellow by Cresol Red, orange by Thymol Blue, yellowish orange by basicCresol Red, black by basic Bromothymol Blue and greyish blue by basicThymol Blue.

Infrared absorption spectrum (cm⁻¹) 3600-3200, 2970, 2600, 2500, 2100,1630 (H₂ O) 1480-1430, 1370-920, 800, 480.

The membrane thus obtained had an ion exchange capacity of 0.70meq/g.dry membrane, an electric resistance of 5.9 Ωcm² and a transportnumber of 0.87. This membrane showed superior resistance to base likethe membrane obtained in Example 16.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (316) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 30

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 15 was immersed in 160 ml of anhydrousdimethoxyethane and, after the addition of 12.4 ml of triethylamine,11.3 ml of N,N-dimethyl-1,3-propanediamine and 11.4 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 72hours. The membrane was taken out and dried under reduced pressure at60° C. for 24 hours, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3350, 2960, 2900, 2860, 2810, 1730,1540, 1470, 1380-1040, 980, 930, 800-500.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (115) identified hereinafter. The ratioof p'/q' was about 7.6.

The amide-type polymer membrane thus obtained was immersed in 300 ml ofanhydrous tetrahydrofuran under an argon atmosphere, and 4.5 g of sodiumborohydride was added thereto. Then, 9 ml of a boron trifluoride ethylether complex was dropwise added in 35 minutes under cooling with icewater and stirred for 1.5 hours. Then, the mixture was stirred at roomtemperature for 30 minutes and further refluxed under heating for 17hours. After cooling, the membrane was taken out and washed in methanolunder reflux for 22 hours, whereby an amine-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3320, 2950, 2870, 2840, 2790, 2400,1470, 1330-1020, 980, 830, 820-480.

The absorption at 1720 cm⁻¹ disappeared, thus indicating that thereduction proceeded completely. The conversion was about 80%. Thismembrane was not dyeable with basic Thymol Blue or basic BromothymolBlue, but it was dyed yellow by Cresol Red, yellowish orange by ThymolBlue and blue by Bromothymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units represented by the formula (215) identified hereinafter.The ratio of p'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of N,N-dimethylformamide and heated at 60° C. for 72hours, whereby an ammonium iodide-type polymer membrane was obtained.Then, this membrane was immersed in 250 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 28 hours (the solution wasreplaced at an intermediate point of this operation). Thereafter, themembrane was immersed in methanol and washed at 60° C. for 19 hours,whereby an ammonium chloride-type polymer membrane was obtained. Thismembrane was not dyeable with basic Thymol Blue, but it was dyed yellowby Cresol Red, orange by Thymol Blue and Bromothymol Blue and dark redby basic Cresol Red.

Infrared absorption spectrum (cm⁻¹) 3400, 3020, 2950, 2820, 2400, 1630,1470, 1380-1020, 970, 895, 840, 820-470.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (317) identified hereinafter. The ratioof p'/q' was about 7.6. The membrane thus obtained had an ion exchangecapacity of 1.15 meq/g.dry membrane, an electric resistance of 1.7 Ωcm²and a transport number of 0.85.

EXAMPLE 31

A carboxylic acid-type polymer membrane (12 cm²) obtained in the samemanner as in Example 15, was immersed in 40 ml of methyl orthoformateand heated at 70° C. for 2.5 hours. The membrane was taken out and driedunder reduced pressure at 60° C. for 19 hours, whereby a methylester-type polymer membrane was obtained. In the infrared absorptionspectrum, this membrane showed strong absorption by carbonyl at 1780cm⁻¹. Further, dyeability of this membrane was examined with use ofCrystal Violet, whereby it was found that the membrane was not dyeable.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (1) identified hereinafter, wherein W wasa methoxy group. The ratio of p'/q' was about 7.6.

The methyl ester-type polymer membrane (42 cm²) thus obtained, wasimmersed in 160 ml of anhydrous dimethoxyethane and, after the additionof 12.4 ml of triethylamine, 11.3 ml of N,N'-dimethyl-1,3-propanediamineand 11.4 ml of trimethylchlorosilane, heated under an argon atmosphereat 90° C. for 72 hours. The membrane was taken out and dried underreduced pressure at 60° C. for 24 hours, whereby an amide-type polymermembrane was obtained. The infrared absorption spectrum of this membranewas substantially the same as the spectrum of the amide-type membraneobtained in Example 30.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (115) identified hereinafter. The ratioof p'/q' was about 7.6.

The amide-type polymer membrane thus obtained was immersed in 300 ml ofanhydrous tetrahydrofuran under an agron atmosphere, and 4.5 g of sodiumborohydride was added. Then, 9 ml of a boron trifluoride ethyl ethercomplex was added dropwise in 35 minutes under cooling with ice water,and stirred for 1.5 hours. Thereafter, the mixture was stirred at roomtemperature for 30 minutes and further refluxed under heating for 17hours. After cooling, the membrane was taken out and washed in methanolunder reflux for 22 hours, whereby an amine-type polymer membrane wasobtained. The infrared absorption spectrum of this membrane wassubstantially the same as the spectrum of the amine-type membraneobtained in Example 30.

The absorption at 1720 cm⁻¹ disappeared, thus indicating that thereduction proceeded completely. The conversion was about 78%. Thismembrane was not dyeable with basic Thymol Blue or basic BromothymolBlue, but it was dyed yellow by Cresol Red, yellowish orange by ThymolBlue and blue by Bromothymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (215) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 32

To a carboxylic acid-type polymer membrane (10 cm²) obtained in the samemanner as in Example 15 were added 4.3 ml ofN,N-diethyl-1,3-diaminopropane, 32 ml of anhydrous acetonitrile, 3.7 mlof triethylamine and 3.5 ml of trimethylchlorosilane, and under an argonatmosphere, the mixture was heated at 80° C. for 96 hours. The membranewas taken out, washed with ether and then dried under reduced pressureat 60° C. for 22 hours, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3350, 2900, 2350, 1720, 1520, 1455,1380-1010, 975, 920, 840, 780-480.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (116) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained, was immersed in 170 ml of anhydroustetrahydrofuran under an argon atmosphere, and 3.0 g of sodiumborohydride was added. Then, a solution of 6 ml of a boron trifluorideethyl ether complex in 10 ml of tetrahydrofuran, was added dropwise in30 minutes under cooling with ice water and stirred for 1.5 hours.Thereafter, the mixture was stirred at room temperature for 30 minutesand further refluxed under heating for 20 hours. The membrane was takenout and washed in methanol under reflux for 20 hours. The membrane wastaken out and dried under reduced pressure at 60° C. for 24 hours,whereby an amine-type polymer membrane was obtained. In the infraredabsorption spectrum of this membrane, the absorption at 1720 cm⁻¹attributable to amide carbonyl disappeared, thus indicating that thereduction to the amine-type membrane proceeded completely. Theconversion was about 93%. This membrane was not dyeable with CrystalViolet, basic Thymol Blue or basic Bromothymol Blue, but it was dyedyellow by Cresol Red, light yellow by basic Cresol Red, yellowish orangeby Thymol Blue and dark blue by bromothymol Blue.

Infrared absorption specturm (cm⁻¹) 3300, 2900, 2350, 1460, 1380-940,790-490.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (216) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLES 33 TO 36

An amine membrane obtained by repeating the first part of the operationof Example 30 and amine membranes obtained in the same manner as inExamples 31 and 32, were respectively subjected to conversion to thequaternary ammonium form and counter ion exchange in the same manner asin Example 30 except that the alkylating agents and the conditions forthe conversion to quaternary ammonium form, as identified in Table 2,were employed. The properties of the membranes thereby obtained wereexamined. The results thereby obtained are shown in Table 2 togetherwith the structures of the membranes.

                                      TABLE 2                                     __________________________________________________________________________                              Final membrane                                                Conversion to quaternary       Ion                                  Ex-       ammonium form                  exchange                             am-       Alkyl-                         capacity                                                                           Electric                        ple                                                                              Starting                                                                             ating    Temp.                                                                             Time                                                                             Main structures                                                                       Dyeing (meq/g.                                                                            resistance                                                                         Transport                  Nos.                                                                             membrane                                                                             agent                                                                             Solvent                                                                            (°C.)                                                                      (hr)                                                                             of copolymers                                                                         tests *1                                                                             dry film)                                                                          (Ω ·                                                           cm.sup.2)                                                                          number                                                                              Durability           __________________________________________________________________________    33 Amine-type                                                                           Ethyl                                                                             Methanol                                                                           60  72 Formula (318)                                                                         CR(b): 0.90 4.0  0.86  --                      membrane as                                                                          iodide                                                                            (8 ml)      p'/q': 7.6                                                                            Deep red                                       obtained in                                                                          (2 ml)                  BTB(b):                                        Example 30                     Deep blue                                   34 Amine-type                                                                           Butyl                                                                             Methanol                                                                           60  72 Formula (319)                                                                         CR(b): Red                                                                           --   5.5  0.87  --                      membrane as                                                                          iodide                                                                            (8 ml)      p'/q': 7.6                                                                            BTB(b):                                        obtained in                                                                          (2 ml)                  Deep blue                                      Example 30                                                                 35 Amine-type                                                                           Methyl                                                                            Dimethyl                                                                           60  72 Formula (317)                                                                         CR: Yellow                                                                           1.10 2.0  0.85  --                      membrane as                                                                          iodide                                                                            formamide   p'/q': 7.6                                                                            TB, BTB:                                       obtained in                                                                          (50 ml)                                                                           (200 ml)            Orange                                         Example 31                     CR(b):                                                                        Dark red                                    36 Amine-type                                                                           Methyl                                                                            Methanol                                                                           60  72 Formula (320)                                                                         CV: Not                                                                              --   4.3  0.86  Superior                membrane as                                                                          iodide                                                                            (80 ml)     p'/q': 7.6                                                                            dyeable                chlorine                obtained in                                                                          (20 ml)                 CR: Yellow             resistance              Example 32                     TB: Orange                                                                    BTB:                                                                          Yellowish                                                                     orange                                                                        CR(b):                                                                        Dark red                                                                      BTB: Blue                                                                     TB(b):                                                                        Light green                                 __________________________________________________________________________     *1:                                                                           CV ... Crystal Violet                                                         CR ... Cresol Red                                                             TB ... Thymol Blue                                                            BTB ... Bromothymol Blue                                                      (B) ... Basic                                                            

EXAMPLE 37

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 15, was immersed in 56 ml of anhydroustriethylamine and heated at 60° C. for 3 hours. The membrane was takenout and dried under reduced pressure at 60° C. for 24 hours, whereby atriethylamine carboxylate-type polymer membrane was obtained. In theinfrared absorption spectrum, the membrane showed strong absorption at1680 cm⁻¹.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (1) identified hereinafter, wherein W wasa hydroxyl group with its hydrogen atom substituted by a triethylammonium group. The ratio of p'/q' was about 7.6.

The triethyl amine carboxylate-type polymer membrane thus obtained, wasimmersed in 160 ml of anhydrous dimethoxyethane and, after the additionof 12.4 ml of triethylamine, 11.3 ml of N,N-dimethyl-1,3-propanediamineand 11.4 ml of trimethylchlorosilane, heated under an argon atmosphereat 90° C. for 72 hours. The membrane was taken out and dried underreduced pressure at 60° C. for 24 hours, whereby an amide-type polymermembrane was obtained. The infrared absorption spectrum of this membranewas substantially the same as the spectrum of the amide-type membraneobtained in Example 30.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (115) identified hereinafter. The ratioof p'/q' was about 7.6.

The amide-type polymer membrane thus obtained was immersed in 300 ml ofanhydrous tetrahdyrofuran under an argon atmosphere, and 4.5 g of sodiumborohydride was added. Then, 9 ml of a boron trifluoride ethyl ethercomplex was added dropwise in 35 minutes under cooling with ice waterand stirred for 1.5 hours. Thereafter, the mixture was stirred at roomtemperature for 30 minutes and further refluxed under heating for 17hours. After cooling, the membrane was taken out and washed in methanolunder reflux for 22 hours, whereby an amine-type polymer membrane wasobtained. The infrared absorption spectrum of this membrane wassubstantially the same as the spectrum of the amine-type membraneobtained in Example 30.

The absorption at 1720 cm⁻¹ disappeared, thus indicating that thereduction proceeded completely. The conversion was about 77%. Thismembrane was not dyeable with basic Thymol Blue or basic BromothymolBlue, but it was dyed yellow by Cresol Red, yellowish orange by ThymolBlue and dark blue by Bromothymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (215) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of N,N-dimethylformamide and heated at 60° C. for 72hours, whereby an ammonium iodide-type polymer membrane was obtained.Then, this membrane was immersed in 250 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 28 hours (the solution wasreplaced at an intermediate point of this operation). Thereafter, themembrane was immersed in methanol and washed at 60° C. for 19 hours,whereby an ammonium chloride-type polymer membrane was obtained. Thismembrane was not dyeable with basic Thymol Blue, but it was dyed yellowby Cresol Red, orange by Thymol Blue or Bromothymol Blue and dark red bybasic Cresol Red. The infrared absorption spectrum of this membrane wassubstantially the same of the spectrum of the membrane obtained inExample 30.

Infrared absorption spectrum (cm⁻¹) 3400, 3020, 2950, 2820, 2400, 1630,1470, 1380-1020, 970, 895, 840, 820-470.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (317) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained had an electric resistance of 2.2 Ωcm² and atransport number of 0.85.

EXAMPLE 38

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 15 was immersed in 170 ml of anhydrousdimethoxyethane and, after the addition of 12.4 ml of triethylamine, 11ml of N,N,N'-trimethyl-1,3-propanediamine and 11.4 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 52hours. The membrane was taken out and dried under reduced pressure at60° C. for 24 hours, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹). 3380, 3200, 2950, 2880, 2840, 2780,2400, 1700, 1655, 1530, 1460, 1420, 1360-1020, 980, 845, 800-460.

This membrane was made of a copolymer composed substantially ofrepeating untis of the formula (117) identified hereinafter. The ratioof p'/q' was about 7.6.

The amido-type polymer membrane thus obtained was reduced in the samemanner as in Example 34, whereby an amine-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 2960, 2880, 2830, 2780, 2400, 1470,1360-1000, 980, 840, 810-460.

The absorption in the vicinity of 1700 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely. The conversion was about 79%.This membrane was not dyeable with basic Cresol Red and basic ThymolBlue, but it was dyed yellow by Cresol Red and orange by Thymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (217) identified hereinafter. The ratioof p'/q' was about 7.6.

The amine-type polymer membrane thus obtained was treated in the samemanner as in Example 37, whereby an ammonium chloride-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3350, 3010, 2950, 2810, 2370, 2120,1630, 1470, 1360-1020, 970, 890, 840, 810-460.

The dyeability of this membrane was the same as in the case of Example37. This membrane was made of a copolymer composed substantially ofrepeating units of the formula (317) identified hereinafter. The ratioof p'/q' was 7.6.

The membrane thus obtained had an ion exchange capacity of 0.84meq/g.dry membrane, an electric resistance of 5.1 Ωcm⁻² and a transportnumber of 0.87.

EXAMPLE 39

A n-butyl ester-type polymer membrane (1.7 cm²) obtained in the samemanner as in Example 21 was immersed in 15 ml of anhydroustetrahydrofuran and after the addition of 0.5 ml ofN,N,N'-trimethyl-1,3-propanediamine, refluxed under heating under anargon atmosphere for 74 hours. The membrane was taken out and driedunder reduced pressure at 60° C. for 20 hours, whereby a light brownopaque amide-type polymer membrane was obtained. The infrared absorptionspectrum of this membrane was substantially the same as the spectrum ofthe membrane obtained in Example 38. Namely, the absorption at 1790 cm⁻¹attributable to the ester disappeared, and absorption by C-H wasobserved at 3000-2800 and 1460 cm⁻¹ and strong absorption attributableto amidocarbonyl was observed at 1700 cm⁻¹. The amide-type membrane thusobtained, was reduced in the same manner as in Example 38, whereby acolorless transparent amine-type polymer membrane was obtained. Theinfrared absorption spectrum of this membrane was substantially the sameas the spectrum of the amine-type membrane obtained in Example 38.Namely, the absorption at 1700 cm⁻¹ attributable to amidocarbonyldisappeared, thus indicating that the reduction to the amine-typemembrane proceeded completely. The conversion was about 70%. Thismembrane was not dyeable with Crystal Violet or basic Thymol Blue, butit was dyed yellow by Cresol Red and orange by Thymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (217) identified hereinafter. The ratioof p'/q' was about 7.6.

The amine-type polymer membrane thus obtained was treated in the samemanner as in Example 37, whereby an ammonium chloride-type polymermembrane was obtained. The infrared absorption spectrum and thedyeability of this membrane were substantially the same as in the caseof Example 37.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (317) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained had an electric resistance of 7.2 Ωcm² and atransport number of 0.87.

EXAMPLE 40

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 13, was immersed in 160 ml of anhydrousacetonitrile and, after the addition of 15.8 ml of triethylamine, 14.4ml of N,N-dimethyl-1,3-propanediamine and 14.7 ml oftrimethylchlorosilane, heated under an argon atmosphere at 80° C. for 72hours. The membrane was taken out and dried under reduced pressure at60° C. for 24 hours, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3600-3000, 3000-2850, 2370, 1700,1580-1400, 1380-880, 860-400.

Except for the mesh portion, this membrane was made of a copolymercomposed substantially of repeating units of the formula (115)identified hereinafter. The ratio of p'/q' was about 6.5.

The amide-type polymer membrane thus obtained was immersed in 300 ml ofanhydrous tetrahydrofuran under an argon atmosphere, and 4.5 g of sodiumborohydride was added. Then, 10 ml of a boron trifluoride ethyl ethercomplex was dropwise added in 35 minutes under cooling with ice waterand stirred for 1.5 hours. Thereafter, the mixture was stirred at roomtemperature for 30 minutes and further refluxed under heating for 17hours. After cooling, the membrane was taken out and washed in methanolunder reflux for 22 hours, whereby an amine-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3300, 2940, 2870, 2840, 2780, 2380,1440, 1360-900, 860-400.

The absorption in the vicinity of 1660 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely. This membrane was not dyeablewith basic Thymol Blue or basic Bromothymol Blue, but it was dyed yellowwith Cresol Red, yellowish orange by Thymol Blue and blue by BromothymolBlue.

Except for the mesh portion, this membrane was made of a copolymercomposed essentially of repeating units of the formula (215) identifiedhereinafter. The ratio of p'/q' was about 6.5.

Then, the membrane thus obtained was immersed in a solution of 50 ml ofmethyl iodide in 200 ml of N,N-dimethylformamide and heated at 60° C.for 72 hours, whereby an ammonium iodide-type polymer membrane wasobtained. Then, the membrane was immersed in 250 ml of a 10% methanolsolution of lithium chloride and heated at 60° C. for 28 hours (thesolution was replaced at an intermediate point of this procedure).Thereafter, the membrane was immersed in methanol and washed at 60° C.for 19 hours, whereby an ammonium chloride-type polymer membrane wasobtained. This membrane was not dyeable with basic Thymol Blue, but itwas dyed yellow by Cresol Red, orange by Thymol Blue or Bromothymol Blueand dark red by basic Cresol Red.

Infrared absorption spectrum (cm⁻¹) 3600-3100, 3050-2050, 1620,1520-400.

Except for the mesh portion, this membrane was made of a copolymercomposed substnatially of repeating units of the formula (317)identified hereinafter. The ratio of p'/q' was about 6.5.

The membrane thus obtained had an electric resistance of 2.7 Ωcm² and atransport number of 0.85.

EXAMPLE 41

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 24, was immersed in 160 ml of anhydrousacetonitrile and, after the addition of 12.4 ml of triethylamine, 11.3ml of N,N-dimethyl-1,3-propanediamine and 11.4 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 72hours. The membrane was taken out and dried under reduced pressure at60° C. for 24 hours, whereby an amide-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3350, 2950, 2860, 2830, 2780, 2380,1710, 1530, 1465, 1380-1080, 1060, 1035, 1020, 980, 910, 860, 790, 760,730, 630.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (118) identified hereinafter. The ratioof p'/q' was about 6.4.

The amide-type polymer membrane thus obtained was reduced in the samemanner as in Example 30, whereby an amine-type polymer membrane wasobtained.

Infrared absorption spectrum (cm⁻¹) 3310, 2960, 2870, 2830, 2780, 2400,1725, 1465, 1400-1080, 1040, 975, 630, 550, 510.

The absorption in the vicinity of 1710 cm⁻¹ disappeared, thus indicatingthat the reduction proceeded completely. The dyeability of the membranewas substantially the same as the amine-type membrane obtained inExample 30.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (218) identified hereinafter. The ratioof p'/q' was about 6.4.

Then, the amine-type polymer membrane thus obtained was treated in thesame manner as in Example 30, whereby an ammonium chloride-type polymermembrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3400, 3030, 2970, 2380, 1640, 1490,1380-1080, 980, 890, 820-460.

The dyeability of the membrane was substantially the same as in the caseof Example 30.

The membrane thus obtained, had an electric resistance of 1.2 Ωcm² and atransport number of 0.85.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (321) identified hereinafter. The ratioof p'/q' was about 6.4.

EXAMPLE 42

A carboxylic acid-type polymer membrane obtained in the same manner asin Example 24 was heated in phosphorus pentachloride/phosphorusoxychloride (weight ratio of 1/1.6) at 120° C. for 24 hours. Themembrane was washed in carbon tetrachloride, and then dried. In theinfrared spectrum, this membrane showed strong absorption by carbonyl at1800 cm⁻¹.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (2) identified hereinafter, wherein W wasa chlorine atom. The ratio of p'/q' was about 6.4.

The acid chloride-type polymer membrane (1.7 cm²) thus obtained, wasimmersed in 15 ml of anhydrous tetrahydrofuran and, after the additionof 0.5 ml of N,N-dimethyl-1,3-propanediamine, refluxed under heatingunder an argon atmosphere for 74 hours. The membrane was taken out anddried under reduced pressure at 60° C. for 20 horus, whereby a lightbrown opaque amide-type polymer membrane was obtained. The infraredabsorption spectrum of this membrane was substantially the same as themembrane obtained in Example 41. Namely, the absorption at 1800 cm⁻¹attributable to the acid chloride, disappeared. Then, the amide-typemembrane thus obtained, was reduced in the same manner as in Example 30,whereby a colorless transparent amine-type polymer membrane wasobtained. The infrared absorption spectrum of this membrane wassubstantially the same as the spectrum of the amine-type membraneobtained in Example 41. Namely, the absorption at 1700 cm⁻¹ attributableto amide carbonyl, disappeared, thus indicating that the reduction tothe amine-type membrane proceeded completely. The conversion was about78%. This membrane was not dyeable with Crystal Violet or basic ThymolBlue, but it was dyed yellow by Cresol Red and orange by Thymol blue.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (218) identified hereinafter. The ratioof p'/q' was about 6.4.

Then, the amine-type polymer membrane thus obtained, was treated in thesame manner as in Example 30, whereby an ammonium chloride-type polymermembrane was obtained. The infrared absorption spectrum of this membranewas substantially the same as the spectrum of the membrane obtained inExample 41. The dyeability of the membrane was the same in the case ofExample 30.

Infrared absorption spectrum (cm⁻¹) 3400, 3030, 2970, 2380, 1640, 1490,1380-1080, 980, 890, 820-460.

The membrane thus obtained had an electric resistance of 1.3 Ωcm² and atransport number of 0.85.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (321) identified hereinafter. The ratioof p'/q' was about 6.4.

EXAMPLE 43

An amide-type polymer membrane was obtained in the same manner as inExample 36 except that N,N-diethyl-1,3-diaminopropane as the base aminewas replaced by 2.9 ml of N-(3-aminopropyl)-2-pipecoline.

Infrared absorption spectrum (cm⁻¹) 3280, 2900, 2350, 1720, 1530, 1450,1380-960, 930, 840-495.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (119) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was reduced in the same manner as in Example36, whereby an amine-type polymer membrane was obtained. The conversionas calculated from the values obtained by the elementary analysis, wasabout 84%. The dyeability of the membrane was substantially the same asthe amine-type membrane obtained in Example 36.

Infrared absorption spectrum (cm⁻¹) 3300, 2880, 2350, 1440, 1370-950,770-480.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (219) identified hereinafter. The ratioof p'/q' was 7.6.

The membrane thus obtained, was then converted to a quaternary ammoniumform in the same manner as in Example 36, whereby an ammoniumchloride-type polymer membrane was obtained. This membrane was notdyeable with Crystal Violet, but it was dyed yellowish orange by CresolRed, orange by Thymol Blue, clear yellow by basic Cresol Red, blue basicBromothymol Blue and yellowish green by basic Thymol Blue.

Infrared absorption spectrum (cm⁻¹) 3600-3150, 3020-2850, 2750-2350,1620 (H₂ O) 1480-930, 780-490.

The membrane thus obtained, had an electric resistance of 7.2 Ωcm² and atransport number of 0.87. This membrane also showed superior durability.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (322) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 44

A tubular carboxylic acid-type copolymer (50 cm) obtained in the samemanner as in Example 26, was immersed in 160 ml of anhydrousacetonitrile to fill the tube with the solvent and, after the additionof 12.4 ml of triethylamine, 11.3 ml of N,N-dimethyl-1,3-propanediamineand 11.4 ml of trimethylchlorosilane, heated under an argon atmosphereat 90° C. for 72 hours. The tube was taken out and dried under reducedpressure at 60° C., whereby a tubular amide-type polymer was obtained.The infrared absorption spectrum of the tubular amide-type polymer thusobtained, was substantially the same as the spectrum of the amide-typemembrane obtained in Example 30. The conversion rate was 80%. Thetubular polymer thus obtained, was cut into rings and examined for thedyeability with Crystal Violet, whereby it was found that the polymerwas not dyeable at all.

The amide-type polymer constituting this tube was composed substantiallyof repeating units of the formula (115) identified hereinafter. Theratio of p'/q' was about 6.4.

Under an argon atmosphere, the tubular amide-type polymer thus obtained,was immersed in dried diethylene glycol dimethyl ether so that the tubewas filled with diethylene glycol dimethyl ether. Then, sodiumborohydride was added (a concentration of 0.53M), and the mixture wasthoroughly stirred and cooled. Then, a dried diethylene glycol dimethylether solution of a boron trifluoride ether complex (0.62 mol per mol ofsodium borohydride) was added dropwise under cooling with ice. Thereaction was conducted for 2.5 hours under cooling and for further 21hours at 100° C. The tubular amine-type polymer thereby obtained, waswashed with methanol and dried. The infrared absorption spectrum of thepolymer was substantially the same as the spectrum of the membraneobtained in Example 30. The conversion was 78%. The tubular polymer thusobtained, was cut into rings and examined for the dyeability, whereby itwas found that the polymer had the same dyeability as in the case ofExample 30.

This amine-type polymer was composed substantially of repeating units ofthe formula (215) identified hereinafter. The ratio of p'/q' was about6.4.

The tubular amine-type polymer was then immersed in a solution of methyliodide in methanol (volume ratio of 1/4) and reacted at 60° C. for 50hours. The tubular polymer thereby obtained, was washed with methanoland reacted in a methanol solution of lithium chloride (concentration of1.28 mols) at 60° C. for 24 hours. This tubular polymer was heated inmethanol at 60° C., whereby a desired tubular ammonium chloride-typepolymer was obtained. The tubular polymer thus obtained was not dyeablewith basic Thymol Blue, but was dyed yellow by Cresol Red, orange byThymol Blue and Bromothymol Blue, and dark red by basic Cresol Red.Thus, the presence of anion exchange groups was confirmed.

The tubular anion exchanger thus obtained had an ion exchange capacityof 1.09 meq/g.dry resin. No change was observed in this value even whenthe anion exchanger was treated in methanol at 65° C. for 48 hours,followed by the removal of the solvent under vacuum at 40° C., and thisoperation was repeated 5 times.

This tubular copolymer was composed substantially of repeating units ofthe formula (317) identified hereinafter. The ratio of p'/q' was about6.4.

EXAMPLE 45

A powder carboxylic acid-type copolymer (1.0 g) obtained in the samemanner as in Example 27 was immersed in 160 ml anhydrous dimethoxyethaneand after the addition of 12.4 ml of triethylamine, 11.3 ml ofN,N-dimethyl-1,3-propanediamine and 11.4 ml of trimethylchlorosilane,heated under an argon atmosphere at 90° C. for 72 hours. The powder wascollected by filtration and dried under reduced pressure at 60° C.,whereby a powder amido-type polymer was obtained. The infraredabsorption spectrum of the powder amide-type polymer thus obtained, wassubstantially the same as the amido-type membrane obtained in Example30. The conversion was 75%. The powder polymer was not dyeable withCrystal Violet.

The amido-type polymer constituting this powder was composedsubstantially of repeating units of the formula (115) identifiedhereinafter. The ratio of p'/q' was about 6.6.

The powder amide-type polymer thus obtained, was subjected to thereduction by diborane in the same manner as in Example 30, and thepowder was collected by filtration, whereby a powder amine-type polymerwas obtained. The conversion was 72%. The powder thus obtained wasformed into a KBr disc and examined for the infrared absorptionspectrum. The absorption in the vicinity of 1700 cm⁻¹ attributable toamide carbonyl, completely disappeared.

This powder was not dyeable with basic Thymol Blue or basic BromothymolBlue, but it was dyed yellow by Cresol Red, yellowish orange by ThymolBlue and blue by Bromothymol Blue.

This amine-type polymer was composed substatially of repeating units ofthe formula (215) identified hereinafter. The ratio of p'/q' was about6.6.

The powder amine-type polymer thus obtained, was immersed in a solutionof methyl iodide in methanol (volume ratio of 1/4) and reacted at 60° C.for 50 hours. The powder polymer thus obtained, was washed with methanoland reacted in a methanol solution of lithium chloride (concentration of1.28M) at 60° C. for 24 hours. This powder polymer was heated inmethanol at 60° C., whereby a desired powder ammonium chloride-typepolymer was obtained. The powder polymer thus obtained, was dyed yellowby neutral Cresol Red, dark red by basic Cresol Red and orange by ThymolBlue or Bromothymol Blue. Thus, the presence of anion exchange groupswas confirmed.

The powder anion exchanger thus obtained, had an ion exchange capacityof 0.96 meq/g.dry resin. No change was observed in this value even whenthe anion exchanger was treated in methanol at 65° C. for 48 hours,followed by the removal of the solvent under vacuum at 40° C., and thisoperation was repeated 5 times. This membrane was made of a copolymercomposed substantially of repeating units of the formula (317)identified hereinafter. The ratio of p'/q' was about 6.6.

EXAMPLE 46

The n-butyl ester-type polymer membrane (3 cm²) obtained in the samemanner as in Example 21 was immersed in 20 ml of anhydroustetrahdrofuran and, after the addition of 1 ml of N-methylpiperadine,refluxed under heating under an argon atmosphere for 75 hours. Themembrane was taken out and dried under reduced pressure at 60° C. for 24hours, whereby a light brown opaque amido-type polymer membrane wasobtained. In the infrared absorption spectrum of this membrane, theabsorption at 1790 cm⁻¹ attributable to ester carbonyl completelydisappeared. Absorption by C--H was observed at 3000-2800 and 1450 cm⁻¹,and strong absorption attributable to amide carbonyl was observed at1700 cm⁻¹.

Infrared absorption spectrum (cm⁻¹) 3410, 2960, 2870, 2820, 2400, 1700,1615, 1450, 1390-1040, 980, 890, 850, 820-460.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (110) identified hereinafter. The ratioof p'/q' was about 7.6.

The membrane thus obtained was immersed in 55 ml of anhydroustetrahydrofuran under an argon atmosphere, and 1.5 g of sodiumborohydride was added. Then, a solution of 3 ml of a boron trifluorideethyl ether complex in 5 ml of tetrahydrofuran, was dropwise added in 30minutes under cooling with ice water and stirred for 1.5 hours.Thereafter, the mixture was stirred at room temperature for 30 minutesand further refluxed under heating for 17 hours. The membrane was takenout and washed in methanol under reflux for 20 hours and then driedunder reduced pressure at 60° C. for 24 hours, whereby a light browntransparent amine-type polymer membrane was obtained. In the infraredabsorption spectrum of this membrane, the absorption at 1700 cm⁻¹attributable to amide carbonyl disappeared, thus indicating that thereduction to the amine-type membrane proceeded completely. Theconversion was about 74%. This membrane was not dyeable with CrystalViolet, basic Cresol Red or basic Thymol Blue, but it was dyed yellow byCresol Red and orange by Thymol Blue.

Infrared absorption spectrum (cm⁻¹) 2930, 2880, 2800, 2700, 2350, 1450,1405, 1370, 1360-1020, 1010, 970, 905, 825, 810-460.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (210) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 47

A methyl ester-type polymer membrane (2 cm²) obtained in the same manneras in Example 31 was immersed in 20 ml of anhydrous diethyl ether and,after the addition of 1 ml of N-methylpiperazine, refluxed under heatingunder an argon atmosphere for 21 hours. The membrane was taken out anddried under reduced pressure at 60° C., whereby a colorless translucentamide-type polymer membrane was obtained. The infrared absorptionspectrum of this membrane was substantially the same as the amide-typemembrane obtained in Example 46. This membrane was made of a copolymercomposed substantially of repeating units of the formula (110)identified hereinafter.

The membrane thus obtained, was immersed in 30 ml of anhydrous ethyleneglycol dimethyl ether under an argon atmosphere, and 1 g of sodiumborohydride was added. Then, a solution of 2 ml of a boron trifluorideethyl ether complex in 5 ml of diethylene glycol dimethyl ether, wasadded dropwise in 30 minutes under cooling with ice water and stirredfor 3 hours. Thereafter, the mixture was stirred at room temperature for1 hour and at 100° C. for further 17 hours. Then, the membrane wassubjected to the same post-treatment as in Example 46, whereby anamine-type polymer membrane was obtained. The conversion was about 66%.This membrane was made of a copolymer composed substantially ofrepeating units of the formula (210) identified hereinafter.

EXAMPLES 48 TO 50

The reaction was conducted under the same conditions as in Example 16except that the reaction was carried out in acetonitrile, toluene ortetrahydrofuran instead of dimethoxyethane, whereby an amine-typepolymer membrane was obtained at the conversion as identified in Table3. The dyeability of each of the membranes thereby obtained, wassubstantially the same as in the case where dimethoxyethane was used.The reaction conditions in the Table represent the amidation conditions,and the conversion given in the Table was calculated from the valuesobtained by the elementary analysis of each of the amine-type polymermembranes after the reduction.

                                      TABLE 3                                     __________________________________________________________________________    Surface                                                                       area of the                                                                              Amidation conditions                                                    starting     N--methyl-                                                                          Triethyl-                                                                          Trimethyl                                                                            Temper- Conversion                        Example                                                                            membrane                                                                            Solvent                                                                              piperazine                                                                          amine                                                                              chlorosilane                                                                         ature                                                                              Time                                                                             (roughly)                         Nos. (cm.sup.2)                                                                          (ml)   (mmol)                                                                              (mmol)                                                                             (mmol) (°C.)                                                                       (hr)                                                                             (%)                               __________________________________________________________________________    48   1.5   Acetonitrile                                                                         4.5   4.5  4.5    80   65 74                                           (15)                                                               49   2.0   Toluene                                                                              4.5   4.5  4.5    80   70 65                                           (15)                                                               50   1.5   Tetrahydro-                                                                          4.5   4.5  4.5    65   68 53                                           furan (20)                                                         __________________________________________________________________________

EXAMPLE 51

A carboxylic acid-type polymer membrane (1.5 cm²) obtained in the samemanner as in Example 15 was immersed in 15 ml of anhydrousdimethoxyethane and, after the addition of 0.6 ml ofhexamethyldisilazane, 0.5 ml of methylpiperazine and three drops oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 48hours, whereby an amido-type polymer membrane was obtained. Thismembrane was made of a copolymer composed substantially of repeatingunits of the formula (110) identified hereinafter.

Then, the membrane was reduced in the same manner as in Example 46,whereby an amine-type polymer membrane was obtained. The membrane wasmade of a copolymer composed substantially of repeating units of theformula (210) identified hereinafter. The conversion was about 49%.

EXAMPLE 52

A carboxylic acid-type polymer membrane (1.5 cm²) obtained in the samemanner as in Example 15 was immersed in 3 ml ofN-methyl-N'-(trimethylsilyl)peperazine and heated under an argonatmosphere at from 60° to 65° C. for 48 hours, whereby an amido-typepolymer membrane was obtained. The membrane was made of a copolymercomposed substantially of repeating units of the formula (110)identified hereinafter.

Then, the membrane was reduced in the same manner as in Example 46,whereby an amine-type polymer membrane was obtained. The membrane wasmade of a copolymer composed substantially of repeating units of theformula (210) identified hereinafter. The conversion was about 53%.

EXAMPLE 53

A carboxylic acid-type polymer membrane (1.5 cm²) obtained in the samemanner as in Example 15 was immersed in 15 ml of anhydrousdimethoxyethane and, after the addition of 0.6 ml ofN,O-bis(trimethylsilyl)acetoamide and 0.5 ml ofN,N,N'-trimethylethylenediamine, heated under an argon atmosphere at 90°C. for 48 hours, whereby an amide-type polymer membrane was obtained.The membrane was made of a copolymer composed substantially of repeatingunits of the formula (111) identified hereinafter.

Then, the amido-type polymer membrane thus obtained was reduced in thesame manner as in Example 46, whereby an amine-type polymer membrane wasobtained. The membrane was made of a copolymer composed substantially ofrepeating units of the formula (211) identified hereinafter. Theconversion was about 70%.

EXAMPLE 54

A triethylammonium carboxylate-type polymer membrane obtained byrepeating the first part of the operation of Example 37, was immersed in33 ml of anhydrous dimethoxyethane and, after the addition of 1.86 ml oftriethylamine, 1.5 ml of N,N,N'-trimethylethylenediamine and 1.71 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 64hours, whereby an amide-type polymer membrane was obtained. The membranewas made of a copolymer composed essentially of repeating units of theformula (111) identified hereinafter.

Then, the membrane was reduced in the same manner as in Example 46,whereby an amine-type polymer membrane was obtained. The conversion wasabout 85%. The infrared absorption spectrum and the dyeability of themembrane thereby obtained, were substantially the same as those of themembrane obtained in Example 21.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (211) identified hereinafter. The ratioof p'/q' was about 7.6.

EXAMPLE 55

A methyl ester-type polymer membrane (1.5 cm²) obtained by repeating thefirst part of the operation of Example 31, was immersed in 33 ml ofanhydrous dimethoxyethane and, after the addition of 1.86 ml of triethylamine, 1.5 ml of N,N,N'-trimethylethylenediamine and 1.71 ml oftrimethylchlorosilane, heated under an argon atmosphere at 90° C. for 64hours, whereby an amide-type polymer membrane was obtained. The membranewas made of a copolymer composed substantially of repeating units of theformula (111) identified hereinafter.

Then, the membrane was reduced in the same manner as in Example 46,whereby an amine-type polymer membrane was obtained. The conversion wasabout 84%. The infrared spectrum and the dyeability of the membrane thusobtained, were substantially the same as those of the membrane obtainedin Example 21, thus indicating that membrane was made of the samecopolymer.

EXAMPLE 56

A carboxylic acid-type polymer membrane (42 cm²) obtained in the samemanner as in Example 15 was immersed in 140 ml of anhydrous acetonitrileand, after the addition of 12.4 ml of triethylamine, 13.0 ml ofN,N-dimethyl-1,4-butanediamine and 11.4 ml of tirmethylchlorosilane,heated under an argon atmosphere at 80° C. for 80 hours. The membranewas taken out and dried under reduced pressure at 60° C. for 24 hours,whereby an amide-type polymer membrane was obtained.

Infrared absorption spectrum (cm⁻¹) 3350, 2970, 2900, 2860, 2810, 1730,1540, 1480, 1400, 1040, 980, 930, 800-500.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (120) identified hereinafter. The ratioof p'/q' was about 7.6.

The amide-type polymer membrane thus obtained was immersed in 300 ml ofanhydrous tetrahydrofuran under an argon atmosphere, and 4.5 g of sodiumborohydride was added thereto. Then, 9 ml of a boron trifluoride ethylether complex was added dropwise in 35 minutes under cooling with icewater and stirred for 2 hours. Then, the mixture was stirred at roomtemperature for 30 minutes and further refluxed under heating for 20hours. After cooling, the membrane was taken out and washed in aqueousmethanol at 60° C. for 15 hours, whereby an amine-type polymer membranewas obtained.

Infrared absorption spectrum (cm⁻¹) 3330, 2950, 2870, 2840, 2790, 2400,1480, 1350-1020, 980, 830, 820-480.

The absorption at 1720 cm⁻¹ disappeared, thus indicating that thereduction proceeded completely. The conversion was about 70%. Thismembrane was not dyeable with basic Thymol Blue or basic BromothymolBlue, but it was dyed yellow by Cresol Red, yellowish orange by ThymolBlue and blue by Bromothymol Blue.

This membrane was made of a copolymer composed substantially ofrepeating units represented by the formula (220) identified hereinafter.The ratio of p'/q' was about 7.6.

The membrane thus obtained was immersed in a solution of 50 ml of methyliodide in 200 ml of N,N-dimethylformamide and heated at 60° C. for 80hours, whereby an ammonium iodide-type polymer membrane was obtained.Then, this membrane was immersed in 250 ml of a 10% methanol solution oflithium chloride and heated at 60° C. for 28 hours (the solution wasrenewed at an intermediate point of this operation). Thereafter, themembrane was immersed in methanol and washed at 60° C. for 19 hours,whereby an ammonium chloride-type polymer membrane was obtained. Thismembrane was not dyeable with basic Thymol Blue, but it was dyed yellowby Cresol Red, orange by Thymol Blue and Bromothymol Blue and dark redby basic Cresol Red.

Infrared absorption spectrum (cm⁻¹) 3400, 3030, 2950, 2820, 2400, 1630,1480, 1400-1020, 970, 895, 840, 820-470.

This membrane was made of a copolymer composed substantially ofrepeating units of the formula (323) identified hereinafter. The ratioof p'/q' was about 7.6. The membrane thus obtained had an ion exchangecapacity of 0.99 meq/g.dry membrane, an electric resistance of 3.8 Ωcm²and a transport number of 0.86.

It was observed throughout Examples that physical characteristicsincluding the physical strength, the dimension stability and theflexibility of each starting material perfluorocarbon polymer having thependant terminal group of formula IV were preserved in the resultingquaternary ammonium-type, amine-type and amide-type fluorocarbonpolymers.

REFERENCE EXAMPLE

By using ammonium chloride-type membranes obtained in Examples 30 and40, electrolysis of hydrochloric acid was conducted. For the purpose ofcomparison, electrolysis of hydrochloric acid was conducted in the samemanner by using a commercially available hydrocarbon-type anion exchangemembrane. The conditions for the electrolysis were as follows.

Membrane surface area: 9.6 cm²

Electrode: Platinum

Electrolytes: Anode/Cathode=6N HCl/6N HCl

Current density: 5 A/dm²

The results thereby obtained are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                    Membrane                                                          Membranes   resistance (μ · cm.sup.2)                                                       Cell voltage (V)                                    ______________________________________                                        Membrane of           1.7     1.44                                            Example 30                                                                    Membrane of           2.7     1.48                                            Example 40                                                                    Commercial  about     2.5     1.49                                            membrane                                                                      ______________________________________                                         ##STR62##

We claim:
 1. A quaternary ammonium group containing fluorocarbon polymer comprising a perfluorocarbon main chain and a fluorinated pendant chain of the formula:wherein: X is fluorine, chlorine or --CF₃, l is an integer of 0 to 5, m is 0 or 1, n is an integer of 1 to 5 and Q is selected from the group consisting of: ##STR63## wherein R¹ and R² are lower alkyl, aromatic, hydroxy lower alkyl or R¹ and R² together form tetramethylene or pentamethylene, R³, R⁴ and R⁸ are lower alkyl, R⁵ is hydrogen or lower alkyl or together form tetramethylene or pentamethylene, a is an integer of 3 to 5 and Z is a counter ion for the quaternary ammonium ion.
 2. The fluorocarbon polymer according to claim 1, wherein the main chain is a linear perfluorocarbon random polymer chain comprising repeating units represented by the formula: ##STR64## where p is an integer of 3 to 16, q is an integer of 1 to 10, and the ratio of p'/q' is within a range of from 2 to 16 where p' is an average value of all p in the repeating units and q' is an average value of all q in the repeating units.
 3. The fluorocarbon polymer according to claim 1, wherein Q is: ##STR65##
 4. The fluorocarbon polymer according to claim 1, wherein Q is selected from the group consisting of ##STR66##
 5. The quaternary ammonium group containing fluorocarbon polymer of claim 1 wherein Q is selected from the group consisting of: ##STR67##
 6. An anion exchange membrane comprising a fluorocarbon polymer having a perfluorocarbon main chain and a fluorinated pendant chain of the formula: ##STR68## wherein: X is fluorine, chlorine or --CF₃, l is an integer of 0 to 5, m is 0 or 1, n is an integer of 1 to 5 and Q is selected from the group consisting of: ##STR69## wherein R¹ and R² are lower alkyl, aromatic, hydroxy lower alkyl or R¹ and R² together form tetramethylene or pentamethylene, R³, R⁴ and R⁸ are lower alkyl, R⁵ is hydrogen or lower alkyl and R⁶ and R⁷ are lower alkyl or together form tetramethylene or pentamethylene, a is an integer of 3 to 5 and Z is a counter ion for the quaternary ammonium ion.
 7. The anion exchange membrane of claim 6, wherein Q is selected from the group consisting of: ##STR70##
 8. The anion exchange membrane of claim 6 wherein the main chain is a linear perfluorocarbon random polymer chain comprising repeating units represented by the formula: ##STR71## where p is an integer of 3 to 16, q is an integer of 1 to 10, and the ratio of p'/q' is within a range of from 2 to 16 where p' is an average value of all p in the repeating units and q' is an average value of all q in the repeating units.
 9. The anion exchange polymer of claim 6, which comprises repeating units represented by the formula: ##STR72## where p is an integer of 3 to 16, q is an integer of q to 10, and the ration of p'/q' is within a range of from 2 to 16 where p' is an average value of all p in the repeating units and q' is an average value of all q in the repeating units.
 10. The anion exchange membrane of claim 6 wherein Q is: ##STR73##
 11. The anion exchange membrane of claim 6, wherein Q is selected from the group consisting of: ##STR74##
 12. The anion exchange membrane according to claim 6, which is in a tubular form. 